Challenges in using siliceous subfossils as a tool for inferring past water level and hydroperiod in Everglades marshes

Successfully rehabilitating drained wetlands through hydrologic restoration is dependent on defining restoration targets, a process that is informed by pre-drainage conditions, as well as understanding linkages between hydrology and ecosystem structure. Paleoecological records can inform restoration goals by revealing long-term patterns of change, but are dependent on preservation of biomarkers that provide meaningful interpretations of environmental change. In the Florida Everglades, paleohydrological hind-casting could improve restoration forecasting, but frequent drying of marsh soils leads to poor preservation of many biomarkers. To determine the effectiveness of employing siliceous subfossils in paleohydrological reconstructions, we examined diatoms, plant and sponge silico-sclerids from three soil cores in the central Everglades marshes. Subfossil quality varied among cores, but the abundance of recognizable specimens was sufficient to infer 1,000–3,000 years of hydrologic change at decadal to centennial resolution. Phytolith morphotypes were linked to key marsh plant species to indirectly measure fluctuations in water depth. A modern dataset was used to derive diatom-based inferences of water depth and hydroperiod (R2 = 0.63, 0.47; RMSE = 14 cm, 120 days, respectively). Changes in subfossil quality and abundances at centennial time-scales were associated with mid-Holocene climate events including the Little Ice Age and Medieval Warm Period, while decadal-scale fluctuations in assemblage structure during the twentieth century suggested co-regulation of hydrology by cyclical climate drivers (particularly the Atlantic Multidecadal Oscillation) and water management changes. The successful reconstructions based on siliceous subfossils shown here at a coarse temporal scale (i.e., decadal to centennial) advocate for their application in more highly resolved (i.e., subdecadal) records, which should improve the ability of water managers to target the quantity and variability of water flows appropriate for hydrologic restoration.

Assessment of the occurrence and potential risks of pharmaceuticals and their metabolites in fish and water using liquid chromatography mass spectrometry

A comprehensive method for the analysis of 11 target pharmaceuticals representing multiple therapeutic classes was developed for biological tissues (fish) and water. Water samples were extracted using solid phase extraction (SPE), while fish tissue homogenates were extracted using accelerated solvent extraction (ASE) followed by mixed-mode cation exchange SPE cleanup and analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS). Among the 11 target pharmaceuticals analyzed, trimethoprim, caffeine, sulfamethoxazole, diphenhydramine, diltiazem, carbamazepine, erythromycin and fluoxetine were consistently detected in reclaimed water. On the other hand, caffeine, diphenhydramine and carbamazepine were consistently detected in fish and surface water samples. In order to understand the uptake and depuration of pharmaceuticals as well as bioconcentration factors (BCFs) under the worst-case conditions, mosquito fish were exposed to reclaimed water under static-renewal for 7 days, followed by a 14-day depuration phase in clean water. Characterization of the exposure media revealed the presence of 26 pharmaceuticals while 5 pharmaceuticals including caffeine, diphenhydramine, diltiazem, carbamazepine, and ibuprofen were present in the organisms as early as 5 h from the start of the exposure. Liquid chromatography ultra-high resolution Orbitrap mass spectrometry was explored as a tool to identify and quantify phase II pharmaceutical metabolites in reclaimed water. The resulting data confirmed the presence of acetyl-sulfamethoxazole and sulfamethoxazole glucuronide in reclaimed water. To my knowledge, this is the first known report of sulfamethoxazole glucuronide surviving intact through wastewater treatment plants and occurring in environmental water samples. Finally, five bioaccumulative pharmaceuticals including caffeine, carbamazepine, diltiazem, diphenhydramine and ibuprofen detected in reclaimed water were investigated regarding the acute and chronic risks to aquatic organisms. The results indicated a low potential risk of carbamazepine even under the worst case exposure scenario. Given the dilution factors that affect environmental releases, the risk of exposure to carbamazepine will be even more reduced.

Relating Freshwater Flow with Estuarine Water Quality in the Southern Everglades Mangrove Ecotone

Florida Bay is more saline than it was historically, and reduced freshwater flows may lead to more phosphorus inputs to the mangrove ecotone from the marine end-member. This is important given plans to restore freshwater flow into eastern Florida Bay. We investigated the relationships between salinity, nutrients, and hydrologic variables in the mangrove ecotone of Taylor Slough. We expected that total phosphorus (TP) would increase with salinity, reflecting a downstream marine source, while total nitrogen (TN) would increase with flow in the mangrove ecotone. Despite expectations of increased flows improving the ecological health of lower Taylor Slough and Florida Bay, total nitrogen (TN) and total phosphorus (TP) dynamics may shift in response to new conditions of flow and salinity as well as organic carbon, N, and P availability. Our results showed that TP concentrations are more discharge-driven while TN is more variable and potentially derived from different sources along the flow path from the freshwater Everglades marshes to Florida Bay. Increased flow of freshwater through Taylor Slough will likely decrease TP concentrations in this historically oligotrophic and P-limited ecosystem. However, more studies along the mangrove ecotone is needed to understand how increased flows will affect nitrogen dynamics relative to phosphorus.

Areal and vertical distribution of total soil mercury and total phosphorusin the southern half of water conservation area 3-A, Everglades, Southern Florida

Total soil-mercury and phosphorus concentrations were determined in 64 sites in the southern half of Water Conservation Area 3A, an area of approximately 500 km2 . Surface soil-Hg concentrations ranged from 117 to 300 ng-g-1;total phosphorus concentrations range from 350 to 850 pg~g-1. No consistent north-south or east-west trends are found in the mercury or phosphorus surface concentrations when they are normalized to soil bulk density. Nine sites were used for the determination of the vertical distribution of soilmercury. Vertical profiles of soil-Hg revealed decreasing concentrations with depth and correlated well with phosphorus in soil profiles. Mercury concentrations in soil profiles may be interpreted as an increase in the rate of deposition of mercury in the region in recent decades and/or as postdepositionalmobilization of mercury to surface layers.

Parallel relationships, architecture and water : the urban spa

This thesis explores the relationship of architecture and water through the design of an urban spa that offers both a bodily and a poetic experience of water. Research included investigation of recent architectural projects that enhance and order the view, sound, and touch of water as well as projects that integrate fountains, showers and reflecting pools into the experience of a building. In the design of the spa, the movement of water was based metaphorically on the natural water cycle: evaporation, condensation and collection of water in pools. The building presents fountains, rivulets, and pools in a descending sequence that represents the natural flow of water. The temperature of water and the activities of the spa follow the same descending sequence, progressing from a warm water bath at the top of the building to cool swimming pool at the plaza level in a contemporary interpretation of the experience of a Roman Bath.

Hydro-Meteorology and Water Budget of the Mara River Basin Under Land Use Change Scenarios

Mara is a transboundary river located in Kenya and Tanzania and considered to be an important life line to the inhabitants of the Mara-Serengeti ecosystem. It is also a source of water for domestic water supply, irrigation, livestock and wildlife. The alarming increase of water demand as well as the decline in the river flow in recent years has been a major challenge for water resource managers and stakeholders. This has necessitated the knowledge of the available water resources in the basin at different times of the year. Historical rainfall, minimum and maximum stream flows were analyzed. Inter and intra-annual variability of trends in streamflow are discussed. Landsat imagery was utilized in order to analyze the land use land cover in the upper Mara River basin. The semi-distributed hydrological model, Soil and Water Assessment Tool (SWAT) was used to model the basin water balance and understand the hydrologic effect of the recent land use changes from forest-to-agriculture. The results of this study provided the potential hydrological impacts of three land use change scenarios in the upper Mara River basin. It also adds to the existing literature and knowledge base with a view of promoting better land use management practices in the basin.

Water temperature reconstructions based on paired Uk'37 and Tex86 records, and paired surface and subsurface Mg/Ca records

This dataset contains the collection of available published paired Uk'37 and Tex86 records spanning multi-millennial to multi-million year time scales, as well as a collection of Mg/Ca-derived temperatures measured in parallel on surface and subsurface dwelling foraminifera, both used in the analyses of Ho and Laepple, Nature Geoscience 2016. As the signal-to-noise ratios of proxy-derived Holocene temperatures are relatively low, we selected records that contain at least the last deglaciation (oldest sample >18kyr BP).

(Tables 1-3) Water chemistry of cloud forest streams at baseflow conditions, Rio San Francisco, Ecuador

We investigated controls on the water chemistry of a South Ecuadorian cloud forest catchment which is partly pristine, and partly converted to extensive pasture. From April 2007 to May 2008 water samples were taken weekly to biweekly at nine different subcatchments, and were screened for differences in electric conductivity, pH, anion, as well as element composition. A principal component analysis was conducted to reduce dimensionality of the data set and define major factors explaining variation in the data. Three main factors were isolated by a subset of 10 elements (Ca2+, Ce, Gd, K+, Mg2+, Na+, Nd, Rb, Sr, Y), explaining around 90% of the data variation. Land-use was the major factor controlling and changing water chemistry of the subcatchments. A second factor was associated with the concentration of rare earth elements in water, presumably highlighting other anthropogenic influences such as gravel excavation or road construction. Around 12% of the variation was explained by the third component, which was defined by the occurrence of Rb and K and represents the influence of vegetation dynamics on element accumulation and wash-out. Comparison of base- and fast flow concentrations led to the assumption that a significant portion of soil water from around 30 cm depth contributes to storm flow, as revealed by increased rare earth element concentrations in fast flow samples. Our findings demonstrate the utility of multi-tracer principal component analysis to study tropical headwater streams, and emphasize the need for effective land management in cloud forest catchments.

A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

Three-dimensional tomographic reconstruction of an exceptionally well preserved ichnological assemblage from the Stainmore Foundation, Carboniferous, UK

This Ph.D. thesis addresses current issues with ichnotaxonomic practice, and characterizes an exceptionally well preserved ichnological assemblage from the Carboniferous Stainmore Formation, Northumberland, United Kingdom. Samples were collected from closely localized float representative of various units throughout the succession, which was deposited in a storm-dominated marine shoreface. Three dominant ichnotaxa were selected for three-dimensional morphological analysis due to their complicated morphology and/or unclear taxonomic status: 1) Dactyloidites jordii isp. nov.; 2) Beaconites capronus, and; 3) Neoeione moniliformis comb. nov. Using serial grinding and photography, these ichnotaxa were ground and modelled in true colour. High-resolution models of three taxa produced in this study are the basis of the first complete three-dimensional consideration of the traces, and forms the basis for refined palaeobiological and ethological analysis of these taxa. Dactyloidites jordii isp. nov. is a stellate to palmate burrow composed of numerous long, narrow rays that exhibit three orders of branching arranged into tiered galleries radiating from a central shaft. It is considered to be the feeding structure produced by a vermiform organism. Beaconites capronus is a winding trace with distinctly chevron-shaped, meniscate backfill demonstrated herein to backfill the vertical shafts associated with its burrows in a comparable fashion to the horizontal portion of the burrow. This lack of a surface connection would result in the trace making organism being exposed to low-oxygen porewater. Coping with this porewater dysoxia could be approached by burrowing organisms in a number of ways: 1) revisiting the sediment-water interface; 2) creating periodic shafts; or 3) employing anaerobic metabolism. Neoeione moniliformis was originally introduced as Eione moniliformis, however, the genus Eione Tate, 1859 is a junior homonym of Eione Rafinesque, 1814. This led to the transfer of Eione moniliformis to Parataenidium. Through careful examination and three-dimensional characterization of topotypes, the transfer to Parataenidium moniliformis is demonstrated herein to be problematic, as Parataenidium refers to primarily horizontal burrows with two distinct layers and Eione moniliformis is composed of one distinct level. As such, the new ichnogenus Neoeione is created to accommodate Neoeione moniliformis.

Experimental investigation of water, snow and granular ice effects on ice failure processes and impact loads

A large series of laboratory ice crushing experiments was performed to investigate the effects of external boundary condition and indenter contact geometry on ice load magnitude under crushing conditions. Four boundary conditions were considered: dry cases, submerged cases, and cases with the presence of snow and granular ice material on the indenter surface. Indenter geometries were a flat plate, wedge shaped indenter, (reverse) conical indenter, and spherical indenter. These were impacted with artificially produced ice specimens of conical shape with 20° and 30° cone angles. All indenter – ice combinations were tested in dry and submerged environments at 1 mm/s and 100 mm/s indentation rates. Additional tests with the flat indentation plate were conducted at 10 mm/s impact velocity and a subset of scenarios with snow and granular ice material was evaluated. The tests were performed using a material testing system (MTS) machine located inside a cold room at an ambient temperature of - 7°C. Data acquisition comprised time, vertical force, and displacement. In several tests with the flat plate and wedge shaped indenter, supplementary information on local pressure patterns and contact area were obtained using tactile pressure sensors. All tests were recorded with a high speed video camera and still photos were taken before and after each test. Thin sections were taken of some specimens as well. Ice loads were found to strongly depend on contact condition, interrelated with pre-existing confinement and indentation rate. Submergence yielded higher forces, especially at the high indentation rate. This was very evident for the flat indentation plate and spherical indenter, and with restrictions for the wedge shaped indenter. No indication was found for the conical indenter. For the conical indenter it was concluded that the structural restriction due to the indenter geometry was dominating. The working surface for the water to act was not sufficient to influence the failure processes and associated ice loads. The presence of snow and granular ice significantly increased the forces at the low indentation rate (with the flat indentation plate) that were higher compared to submerged cases and far above the dry contact condition. Contact area measurements revealed a correlation of higher forces with a concurrent increase in actual contact area that depended on the respective boundary condition. In submergence, ice debris constitution was changed; ice extrusion, as well as crack development and propagation were impeded. Snow and granular ice seemed to provide additional material sources for establishing larger contact areas. The dry contact condition generally had the smallest real contact area, as well as the lowest forces. The comparison of nominal and measured contact areas revealed distinct deviations. The incorporation of those differences in contact process pressures-area relationships indicated that the overall process pressure was not substantially affected by the increased loads.

(Table 1) Salinity and dissolved organic carbon concentration of marine water (ANT-XIX/2) and mangrove porewater (Brazil)

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.

Physical oceanography from 120 CTDs, 79 water bottles stations, and 30 helicopter-borne CTDs during POLARSTERN cruise ANT-XXII/2 (ISPOL)

The Ice Station POLarstern (ISPOL) cruise revisited the western Weddell Sea in late 2004 and obtained a comprehensive set of conductivity-temperature-depth (CTD) data. This study describes the thermohaline structure and diapycnal mixing environment observed in 2004 and compares them with conditions observed more than a decade earlier. Hydrographic conditions on the central western Weddell Sea continental slope, off Larsen C Ice Shelf, in late winter/early spring of 2004/2005 can be described as a well-stratified environment with upper layers evidencing relict structures from intense winter near-surface vertical fluxes, an intermediate depth temperature maximum, and a cold near-bottom layer marked by patchy property distributions. A well-developed surface mixed layer, isolated from the underlying Warm Deep Water (WDW) by a pronounced pycnocline and characterized by lack of warming and by minimal sea-ice basal melting, supports the assumption that upper ocean winter conditions persisted during most of the ISPOL experiment. Much of the western Weddell Sea water column has remained essentially unchanged since 1992; however, significant differences were observed in two of the regional water masses. The first, Modified Weddell Deep Water (MWDW), comprises the permanent pycnocline and was less saline than a decade earlier, whereas Weddell Sea Bottom Water (WSBW) was horizontally patchier and colder. Near-bottom temperatures observed in 2004 were the coldest on record for the western Weddell Sea over the continental slope. Minimum temperatures were ~0.4 and ~0.3 °C colder than during 1992-1993, respectively. The 2004 near-bottom temperature/salinity characteristics revealed the presence of two different WSBW types, whereby a warm, fresh layer overlays a colder, saltier layer (both formed in the western Weddell Sea). The deeper layer may have formed locally as high salinity shelf water (HSSW) that flowed intermittently down the continental slope, which is consistent with the observed horizontal patchiness. The latter can be associated with the near-bottom variability found in Powell Basin with consequences for the deep water outflow from the Weddell Sea.

Multinet and water column properties of station SO225-21

Insight into past changes of upper ocean stratification, circulation, and nutrient signatures rely on our knowledge of the apparent calcification depth (ACD) and ecology of planktonic foraminifera, which serve as archives for paleoceanographic relevant geochemical signals. The ACD of different species varies strongly between ocean basins, but also regionally. We constrained foraminiferal ACDs in the western Pacific warm pool (Manihiki Plateau) by comparing stable oxygen and carbon isotopes (d18Ocalcite, d13Ccalcite) as well as Mg/Ca ratios from living planktonic foraminifera to in-situ physical and chemical water mass properties (temperature, salinity, d18Oseawater, d13CDIC). Our analyses point to Globigerinoides ruber as the shallowest dweller, followed by Globigerinoides sacculifer, Neogloboquadrina dutertrei, Pulleniatina obliquiloculata and Globotaloides hexagonus inhabiting increasingly greater depths. These findings are consistent with other ocean basins; however, absolute ACDs differ from other studies. The uppermost mixed-layer species G. ruber and G. sacculifer denote mean calcification depths of ~95 m and ~120 m, respectively. These Western Pacific ACDs are much deeper than in most other studies and most likely relate to the thick surface mixed layer and the deep chlorophyll maximum in this region. Our results indicate that N. dutertrei appears to be influenced by mixing waters from the Pacific equatorial divergence, while P. obliquiloculata with an ACD of ~160 m is more suitable for thermocline reconstructions. ACDs of G. hexagonus reveal a deep calcification depth of ~450 m in oxygen-depleted, but nutrient-rich water masses, consistent to other studies. As the d13C of G. hexagonus is in near-equilibrium with ambient seawater, we suggest this species is suitable for tracing nutrient conditions in equatorial water masses originating in extra-topical regions.

Sediment and pore water chemistry of cores 214 and 755 recovered during Meteor M72/1 and POSEIDON cruise POS317/2, northwestern Black Sea

High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (SO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate-methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events for which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, 'relict' barite fronts would only be preserved for a few thousands of years, if at all.