Sea-surface temperature reconstruction for sediment core GeoB1023-5

Sediment core GeoB 1023-5 from the eastern South Atlantic was investigated at high temporal resolution for variations of sea-surface temperature (SST) during the past 22 kyr, using the alkenone (UK'37) method. SSTs increased by 3.5°C from about 18°C during the Last Ice Age (21±2 cal kyr BP) to about 21.5°C at 14.5 cal kyr BP. This warming trend associated with the deglaciation phase was followed by a cooling event with lowest SSTs near 20°C, persisting for about 1000 years between 13 and 12 cal kyr BP. The SSTs then continued to increase to about 22.5°C at the Holocene climatic optimum at 7 cal kyr BP, and decreased again during the Late Holocene to a core-top value of 19.8°C that is comparable to modern annual mean SST values. When compared with alkenone SST records from the eastern North Atlantic, our SST record indicates continuous warming throughout the deglaciation phase in the Benguela Current, while its northern counterpart, the Canary Current, experienced prominent cooling during 'Heinrich Event 1' (H1). On the other hand, for the time period corresponding to the 'Younger Dryas' (YD) cooling event, the Benguela SST record exhibits a cold-temperature interval that corresponds to that observed in the eastern North Atlantic SST records. This observation suggests that interhemispheric climate response in Atlantic eastern boundary current systems was different with respect to the two abrupt climate events associated with Termination I. For the H1, the eastern South Atlantic SST record strongly supports the hypothesis that an 'anti-phase' thermal behavior in South Atlantic surface waters was forced by the slowdown of the North Atlantic Deep Water formation during cold spells in the North Atlantic. In contrast, the abrupt cooling in the eastern South Atlantic coincident with the YD period was probably induced by more vigorous global atmospheric circulation, enhancing the upwelling intensity in both eastern boundary current systems. This atmospheric control may have overridden any effect caused by changes in thermohaline circulation on the South Atlantic SSTs during the YD, which leads to the assumption that the thermohaline circulation was already much closer to its interglacial mode during the YD than during the H1.

Sea surface temperatures derived from alkenones from Late Quaternary sediments of the East Equatorial South Atlantic

Angola Basin and Walvis Ridge records of past sea surface temperatures (SST) derived from the alkenone Uk 37 index are used to reconstruct the surface circulation in the east equatorial South Atlantic for the last 200,000 years. Comparison of SST estimates from surface sediments between 5° and 20°S with modern SST data suggests that the alkenone temperatures represent annual mean values of the surface mixed layer. Alkenone-derived temperatures for the warm climatic maxima of the Holocene and the penultimate interglacial are 1 to 4°C higher than latest Holocene values. All records show glacial to interglacial differences of about 3.5°C in annual mean SST, which is about 1.5°C greater than the difference estimated by CLIMAP (1981) for the eastern Angola Basin. At the Walvis Ridge, significant SST variance is observed at all of the Earth's orbital periodicities. SST records from the Angola Basin vary predominantly at 23- and 100-kyr periodicities. For the precessional cycle, SST changes at the Walvis Ridge correspond to variations of boreal summer insolation over Africa and lead ice volume changes, suggesting that the east equatorial South Atlantic is sensitive to African monsoon intensity via trade-wind zonality. Angola Basin SST records lag those from the Walvis Ridge and the equatorial Atlantic by about 3 kyr. The comparison of Angola Basin and Walvis Ridge SST records implies that the Angola-Benguela Front (ABF) (currently at about 14-16°S) has remained fairly stationary between 12° and 20°S (the limits of our cores) during the last two glacial-interglacial cycles. The temperature contrast associated with the ABF exhibits a periodic 23-kyr variability which is coherent with changes in boreal summer insolation over Africa. These observations suggest that surface waters north of the present ABF have not directly responded to monsoon-modulated changes in the trade-wind vector, that the central field of zonally directed trades in the southern hemisphere was not shifted or extended northward by several degrees of latitude during glacials, and that a cyclonic gyre circulation has existed in the east equatorial South Atlantic over the last 200,000 years. This scenario contradicts former assumptions of glacial intensification of the Benguela Current into the eastern Angola Basin and increased coastal upwelling off Angola.

Quantitative composition and distribution of the silt fraction in surface sediments of the North-West African continental margin

Surface sediments from the continental slope and rise of North-West Africa between the Canary lslands and the Cape Verde Islands are mainly composed of silt-sized material (2-63 µm). A number of sampling profiles were run normal to the coast and the composition of the silt fraction was determined quantitatively by scanning electron microscope analysis. The carbonate portion of the sediment was found to be nearly exclusively of biogenic origin. The most important contributors are planktonic foraminifers and coccoliths with minor contributions derived from pteropods. Plankton-produced biogenic opal such as diatoms and radiolarians play a very minor role. The high production rates of opal-silica plankton which exists in the surface waters of the NW-African upwelling system does not give rise to corresponding increases of opal accumulation in the bottom sediment. Benthic producers consist mainly of foraminifers and molluscs but the entire input from benthic producers is extremely small. An exception to this occurs in the prodelta sediments of the Senegal river. Downslope particle transport is indicated by the occurrence of shallow-water coralline algae, ascidian sclerites and cliona boring chips and can be traced as far down as the continental rise. The non-carbonate silt fraction mostly consists of quartz which is derived as eolian dust from the Sahara desert by the Harmattan and the NE-Trade-wind system. The percentage of carbonate in the surface sediments directly indicates the relative proportions of autochthonous biogenic components and terrigenous allochthonous quartz particles.

Dissolved iron measured along surface transects of the CARUSO-EISENEX experiment

Measurements of Fe(II) and H2O2 were carried out in the Atlantic sector of the Southern Ocean during EisenEx, an iron enrichment experiment. Iron was added on three separate occasions, approximately every 8 days, as a ferrous sulfate (FeSO4) solution. Vertical profiles of Fe(II) showed maxima consistent with the plume of the iron infusion. While H2O2 profiles revealed a corresponding minima showing the effect of oxidation of Fe(II) by H2O2, observations showed detectable Fe(II) concentrations existed for up to 8 days after an iron infusion. H2O2 concentrations increased at the depth of the chlorophyll maximum when iron concentrations returned to pre-infusion concentrations (<80 pM) possibly due to biological production related to iron reductase activity. In this work, Fe(II) and dissolved iron were used as tracers themselves for subsequent iron infusions when no further SF6 was added. EisenEx was subject to periods of weak and strong mixing. Slow mixing after the second infusion allowed significant concentrations of Fe(II) and Fe to exist for several days. During this time, dissolved and total iron in the infusion plume behaved almost conservatively as it was trapped between a relict mixed layer and a new rain-induced mixed layer. Using dissolved iron, a value for the vertical diffusion coefficient Kz=6.7±0.7 cm**2/s was obtained for this 2-day period. During a subsequent surface survey of the iron-enriched patch, elevated levels of Fe(II) were found in surface waters presumably from Fe(II) dissolved in the rainwater that was falling at this time. Model results suggest that the reaction between uncomplexed Fe(III) and O2? was a significant source of Fe(II) during EisenEx and helped to maintain high levels of Fe(II) in the water column. This phenomenon may occur in iron enrichment experiments when two conditions are met: (i) When Fe is added to a system already saturated with regard to organic complexation and (ii) when mixing processes are slow, thereby reducing the dispersion of iron into under-saturated waters.

Global database of surface ocean particulate organic carbon export fluxes diagnosed from the 234Th technique

Through the processes of the biological pump, carbon is exported to the deep ocean in the form of dissolved and particulate organic matter. There are several ways by which downward export fluxes can be estimated. The great attraction of the 234Th technique is that its fundamental operation allows a downward flux rate to be determined from a single water column profile of thorium coupled to an estimate of POC/234Th ratio in sinking matter. We present a database of 723 estimates of organic carbon export from the surface ocean derived from the 234Th technique. Data were collected from tables in papers published between 1985 and 2013 only. We also present sampling dates, publication dates and sampling areas. Most of the open ocean Longhurst provinces are represented by several measurements. However, the Western Pacific, the Atlantic Arctic, South Pacific and the South Indian Ocean are not well represented. There is a variety of integration depths ranging from surface to 220m. Globally the fluxes ranged from -22 to 125 mmol of C/m**2/d. We believe that this database is important for providing new global estimate of the magnitude of the biological carbon pump.

Ice rafted debris, planktic foraminifera and reconstructed sea surface temperatures from site GIK23414

Planktic foraminiferal census data, faunal sea surface temperatures (SSTs) and oxygen isotopic and lithic records from a site in the northeast Atlantic were analyzed to study the interglacial dynamics of Marine Isotope Stage (MIS) 11, a period thought to closely resemble the Holocene on the basis of orbital forcing. Interglacial conditions during MIS 11 persisted for approximately 26 ka. After the main deglacial meltwater processes ceased, a 10- to 12-ka-long transitional period marked by significant water mass circulation changes occurred before surface waters finally reached their thermal maximum. This SST peak occurred between 400 and 397 ka, inferred from the abundance of the most thermophilic foraminiferal species and was coincident with lowest sea level according to benthic isotope values. The ensuing stepwise SST decrease characterizes the overall climate deterioration preceding the increase in global ice volume by ab. 3 ka. This cooling trend was followed by a more pronounced cold event that began at 388 ka, and that terminated in the recurrence of icebergs at the site around 382 ka. Because the water mass configuration of early MIS 11 evolved quite differently from that of the early Holocene, there is little evidence that MIS 11 can serve as an appropriate analogue for a future Holocene climate, despite the similarity in some orbital parameters.

Shell preservation of Limacina inflata in surface sediments of the Central and South Atlantic

Over 300 surface sediment samples from the Central and South Atlantic Ocean and the Caribbean Sea were investigated for the preservation state of the aragonitic test of Limacina inflata. Results are displayed in spatial distribution maps and are plotted against cross-sections of vertical water mass configurations, illustrating the relationship between preservation state, saturation state of the overlying waters, and overall water mass distribution. The microscopic investigation of L. inflata (adults) yielded the Limacina dissolution index (LDX), and revealed three regional dissolution patterns. In the western Atlantic Ocean, sedimentary preservation states correspond to saturation states in the overlying waters. Poor preservation is found within intermediate water masses of southern origin (i.e. Antarctic intermediate water (AAIW), upper circumpolar water (UCDW)), which are distinctly aragonite-corrosive, whereas good preservation is observed within the surface waters above and within the upper North Atlantic deep water (UNADW) beneath the AAIW. In the eastern Atlantic Ocean, in particular along the African continental margin, the LDX fails in most cases (i.e. less than 10 tests of L. inflata per sample were found). This is most probably due to extensive "metabolic" aragonite dissolution at the sediment-water interface combined with a reduced abundance of L. inflata in the surface waters. In the Caribbean Sea, a more complex preservation pattern is observed because of the interaction between different water masses, which invade the Caribbean basins through several channels, and varying input of bank-derived fine aragonite and magnesian calcite material. The solubility of aragonite increases with increasing pressure, but aragonite dissolution in the sediments does not simply increase with water depth. Worse preservation is found in intermediate water depths following an S-shaped curve. As a result, two aragonite lysoclines are observed, one above the other. In four depth transects, we show that the western Atlantic and Caribbean LDX records resemble surficial calcium carbonate data and delta13C and carbonate ion concentration profiles in the water column. Moreover, preservation of L. inflata within AAIW and UCDW improves significantly to the north, whereas carbonate corrosiveness diminishes due to increased mixing of AAIW and UNADW. The close relationship between LDX values and aragonite contents in the sediments shows much promise for the quantification of the aragonite loss under the influence of different water masses. LDX failure and uncertainties may be attributed to (1) aragonite dissolution due to bottom water corrosiveness, (2) aragonite dissolution due to additional CO2 release into the bottom water by the degradation of organic matter based on an enhanced supply of organic matter into the sediment, (3) variations in the distribution of L. inflata and hence a lack of supply into the sediment, (4) dilution of the sediments and hence a lack of tests of L. inflata, or (5) redeposition of sediment particles.

Geochemistry of surface sediment samples from the South Atlantic Ocean

The aim of the present study is an evaluation of the applicability of biogenic barium as a proxy for productivity. For this purpose, 190 surface sediment samples from the South Atlantic Ocean were analysed for their barium and aluminium concentrations. Biogenic barium is estimated by subtracting the calculated terrigenous barium (obtained from the terrigenous Ba/Al ratio and the amount of Al in the sample) from the total Ba content in the sample. Based on the accumulation rates of biogenic barium, export production is estimated using three different algorithms proposed by [Paleoceanography 7 (1992) 163, doi:10.1029/92PA00181; Global Biogeochem. Cycles 9 (1995) 289, doi:10.1029/95GB00021; Geomar. Report 38 (1995) 105]. Primary productivity was calculated from these different export productions and compared with measurements of recent primary productivity in the overlying surface waters. Only the primary productions calculated on the basis of the algorithm of [Paleoceanography 7 (1992) 163, doi:10.1029/92PA00181] yield productivity values comparable to those existing in ocean surface waters. This study further reveals that it is not sufficient to use a constant, generally applicable organic carbon/biogenic barium ratio, as is postulated by [Global Biogeochem. Cycles 9 (1995) 289, doi:10.1029/95GB00021]. This ratio has to be assessed regionally. For the sediments of the Cape Basin in the eastern South Atlantic Ocean, a new algorithm is developed which gives plausible primary productivities for the overlying surface waters.

Radium in Arctic surface water

The transpolar drift is strongly enriched in 228Ra accumulated on the wide Arctic shelves with subsequent rapid offshore transport. We present new data of Polarstern expeditions to the central Arctic and to the Kara and Laptev seas. Because 226Ra activities in Pacific waters are 30% higher than in Atlantic waters, we correct 226Ra for the Pacific admixture when normalizing 228Ra with 226Ra. The use of 228Ra decay as age marker critically depends on the constancy in space and time of the source activity, a condition that has not yet adequately been tested. While 228Ra decays during transit over the central basin, ingrowth of 228Th could provide an alternative age marker. The high 228Th/228Ra activity ratio (AR = 0.8-1.0) in the central basins is incompatible with a mixing model based on horizontal eddy diffusion. An advective model predicts that 228Th grows to an equilibrium AR, the value of which depends on the scavenging regime. The low AR over the Lomonosov Ridge (AR = 0.5) can be due to either rapid transport (minimum age without scavenging 1.1 year) or enhanced scavenging. Suspended particulate matter load (derived from beam transmission and particulate 234Th) and total 234Th depletion data show that scavenging, although extremely low in the central Arctic, is enhanced over the Lomonosov Ridge, making an age of 3 years more likely. The combined data of 228Ra decay and 228Th ingrowth confirm the existence of a recirculating gyre in the surface water of the eastern Eurasian Basin with a river water residence time of at least 3 years.

(Table 1) Sea surface temperature reconstruction for eastern equatorial Pacific surface sediment samples

Significant uncertainties persist in the reconstruction of past sea surface temperatures in the eastern equatorial Pacific, especially regarding the amplitude of the glacial cooling and the details of the post-glacial warming. Here we present the first regional calibration of alkenone unsaturation in surface sediments versus mean annual sea surface temperatures (maSST). Based on 81 new and 48 previously published data points, it is shown that open ocean samples conform to established global regressions of Uk'37 versus maSST and that there is no systematic bias from seasonality in the production or export of alkenones, or from surface ocean nutrient concentrations or salinity. The flattening of the regression at the highest maSSTs is found to be statistically insignificant. For the near-coastal Peru upwelling zone between 11-15°S and 76-79°W, however, we corroborate earlier observations that Uk'37 SST estimates significantly over-estimate maSSTs at many sites. We posit that this is caused either by uncertainties in the determination of maSSTs in this highly dynamic environment, or by biasing of the alkenone paleothermometer toward El Niño events as postulated by Rein et al. (2005).

(Table 1) Age determination of surface sediment samples from the North Atlantic

Most seafloor sediments are dated with radiocarbon, and the sediment is assumed to be zero-age (modern) when the signal of atmospheric testing of nuclear weapons is present (Fraction modern (Fm) > 1). Using a simple mass balance, we show that even with Fm > 1, half of the planktonic foraminifera at the seafloor can be centuries old, because of bioturbation. This calculation, and data from four core sites in the western North Atlantic indicate that, first, during some part of the Little Ice Age (LIA) there may have been more Antarctic Bottom Water than today in the deep western North Atlantic. Alternatively, bioturbation may have introduced much older benthic foraminifera into surface sediments. Second, paleo-based warming of Sargasso Sea surface waters since the LIA must lag the actual warming because of bioturbation of older and colder foraminifera.

A legal perspective of integrated surface mining, solid waste landfill reclamation and land conservation

In the area of international environmental law this thesis proposes the formulation of one-step planning and permitting regulation for the integrated utilisation of new surface mines as depositories for municipal solid waste. Additionally, the utilisation of abandoned and currently operated surface mines is proposed as solid waste landfills as an integral step in their reclamation. Existing laws, litigation and issues in the United Kingdom, the U.S. and Canada are discussed because of their common legal system, language and heritage. The critical shortage of approved space for disposal of solid waste has caused an urgent and growing problem for both the waste disposal industry and society. Surface mining can serve three important environmental and societal functions inuring to the health and welfare of the public: (1) providing basic minerals for goods and construction; (20 sequentially, to provide critically needed, safe burial sites for society's wastes, and (3) to conserve land by dual purpose use and to restore derelict land to beneficial surface use. Currently, the first two functions are treated environmentally, and in regulation, as two different siting problems, yet they both are earth-disturbing and excavating industries requiring surface restoration. The processes are largely duplicative and should be combined for better efficiency, less earth disturbance, conservation of land, and for fuller and better reclamation of completed surface mines returning the surfaces to greater utility than present mined land reclamation procedures. While both industries are viewed by a developed society and its communities as "bad neighbours", they remain essential and critical for mankind's existence and welfare. The study offers successful examples of the integrated process in each country. The study argues that most non-fuel surface mine openings, if not already safe, can economically, through present containment technology, be made environmentally safe for use as solid waste landfills. Simultaneously, the procedure safeguards and monitors protection of ground and surface waters from landfill contamination.

Assessment of the occurrence and potential effects of pharmaceuticals and personal care products in South Florida waters and sediments

A LLE-GC-MS method was developed to detect PPCPs in surface water samples from Big Cypress National Park, Everglades National Park and Biscayne National Park in South Florida. The most frequently found PPCPs were caffeine, DEET and triclosan with detected maximum concentration of 169 ng/L, 27.9 ng/L and 10.9 ng/L, respectively. The detection frequencies of hormones were less than PPCPs. Detected maximal concentrations of estrone, 17β-estradiol, coprostan-3-ol, coprostane and coprostan-3-one were 5.98 ng/L, 3.34 ng/L, 16.5 ng/L, 13.5 ng/L and 6.79 ng/L, respectively. An ASE-SPE-GC-MS method was developed and applied to the analysis of the sediment and soil area where reclaimed water was used for irrigation. Most analytes were below detection limits, even though some of analytes were detected in the reclaimed water at relatively high concentrations corroborating the fact that PPCPs do not significantly partition to mineral phases. An online SPE-HPLC-APPI-MS/MS method and an online SPE-HPLC-HESI-MS/MS method were developed to analyze reclaimed water and drinking water samples. In the reclaimed water study, reclaimed water samples were collected from the sprinkler for a year-long period at Florida International University Biscayne Bay Campus, where reclaimed water was reused for irrigation. Analysis results showed that several analytes were continuously detected in all reclaimed water samples. Coprostanol, bisphenol A and DEET's maximum concentration exceeded 10 μg/L (ppb). The four most frequently detected compounds were diphenhydramine (100%), DEET (98%), atenolol (98%) and carbamazepine (96%). In the study of drinking water, 54 tap water samples were collected from the Miami-Dade area. The maximum concentrations of salicylic acid, ibuprofen and DEET were 521 ng/L, 301 ng/L and 290 ng/L, respectively. The three most frequently detected compounds were DEET (93%), carbamazepine (43%) and salicylic acid (37%), respectively. Because the source of drinking water in Miami-Dade County is the relatively pristine Biscayne aquifer, these findings suggest the presence of wastewater intrusions into the delivery system or the onset of direct influence of surface waters into the shallow aquifer.

Assessment of the occurrence and potential risks of antibiotics and their metabolites in South Florida waters using liquid chromatography tandem mass spectrometry

An automated on-line SPE-LC-MS/MS method was developed for the quantitation of multiple classes of antibiotics in environmental waters. High sensitivity in the low ng/L range was accomplished by using large volume injections with 10-mL of sample. Positive confirmation of analytes was achieved using two selected reaction monitoring (SRM) transitions per antibiotic and quantitation was performed using an internal standard approach. Samples were extracted using online solid phase extraction, then using column switching technique; extracted samples were immediately passed through liquid chromatography and analyzed by tandem mass spectrometry. The total run time per each sample was 20 min. The statistically calculated method detection limits for various environmental samples were between 1.2 and 63 ng/L. Furthermore, the method was validated in terms of precision, accuracy and linearity. ^ The developed analytical methodology was used to measure the occurrence of antibiotics in reclaimed waters (n=56), surface waters (n=53), ground waters (n=8) and drinking waters (n=54) collected from different parts of South Florida. In reclaimed waters, the most frequently detected antibiotics were nalidixic acid, erythromycin, clarithromycin, azithromycin trimethoprim, sulfamethoxazole and ofloxacin (19.3-604.9 ng/L). Detection of antibiotics in reclaimed waters indicates that they can't be completely removed by conventional wastewater treatment process. Furthermore, the average mass loads of antibiotics released into the local environment through reclaimed water were estimated as 0.248 Kg/day. Among the surface waters samples, Miami River (reaching up to 580 ng/L) and Black Creek canal (up to 124 ng/L) showed highest concentrations of antibiotics. No traces of antibiotics were found in ground waters. On the other hand, erythromycin (monitored as anhydro erythromycin) was detected in 82% of the drinking water samples (n.d-66 ng/L). The developed approach is suitable for both research and monitoring applications.^ Major metabolites of antibiotics in reclaimed wates were identified and quantified using high resolution benchtop Q-Exactive orbitrap mass spectrometer. A phase I metabolite of erythromycin was tentatively identified in full scan based on accurate mass measurement. Using extracted ion chromatogram (XIC), high resolution data-dependent MS/MS spectra and metabolic profiling software the metabolite was identified as desmethyl anhydro erythromycin with molecular formula C36H63NO12 and m/z 702.4423. The molar concentration of the metabolite to erythromycin was in the order of 13 %. To my knowledge, this is the first known report on this metabolite in reclaimed water. Another compound acetyl-sulfamethoxazole, a phase II metabolite of sulfamethoxazole was also identified in reclaimed water and mole fraction of the metabolite represent 36 %, of the cumulative sulfamethoxazole concentration. The results were illustrating the importance to include metabolites also in the routine analysis to obtain a mass balance for better understanding of the occurrence, fate and distribution of antibiotics in the environment. ^ Finally, all the antibiotics detected in reclaimed and surface waters were investigated to assess the potential risk to the aquatic organisms. The surface water antibiotic concentrations that represented the real time exposure conditions revealed that the macrolide antibiotics, erythromycin, clarithromycin and tylosin along with quinolone antibiotic, ciprofloxacin were suspected to induce high toxicity to aquatic biota. Preliminary results showing that, among the antibiotic groups tested, macrolides posed the highest ecological threat, and therefore, they may need to be further evaluated with, long-term exposure studies considering bioaccumulation factors and more number of species selected. Overall, the occurrence of antibiotics in aquatic environment is posing an ecological health concern.^