The occurrence of selected human pharmaceutical compounds in UK estuaries

This report describes a scoping study conducted in order to establish whether pharmaceutical compounds may be present in UK estuaries. Surface water samples collected from five UK estuaries were analysed for the presence of 14 pharmaceutical compounds selected from the priority lists of the UK Environment Agency and the Oslo and Paris Commission (OSPAR). The pharmaceutical compounds/metabolites clofibric acid, clotrimazole, dextropropoxyphene, diclofenac, ibuprofen, mefenamic acid, propranolol, tamoxifen and trimethoprim were detected at measurable concentrations in the samples collected. The concentrations of erythromycin, lofepramine, paracetamol, sulfamethoxazole and acetyl-sulfamethoxazole were all below the limits of detection of the methods used (between 4 and 20 ng l(-1)). The anti-fungal agent clotrimazole was the most frequently detected at a maximal concentration of 22 ng l(-1) and a median concentration of 7 ng l(-1). The analgesic compound ibuprofen was detected at a maximal concentration of approximately 930 ng l(-1) and a median concentration of 48 ng l(-1), whilst the other pharmaceutical compounds were detected between the limits of detection of the method used and 570 ng l(-1).     

Hydraulics of recirculating well pairs for ground water remediation

Recirculating well pairs are a proven means of implementing bioremediation and may also be useful for applying other in situ ground water remediation technologies. A bromide tracer test was performed to characterize the hydraulic performance of a recirculating well pair installed at Moffett Field, California. In particular, we estimate two important properties of the recirculating well pair: (1) the fraction of captured water that is recycled between the wells, and (2) the travel-time distribution of ground water in the induced zone of recirculation. We also develop theoretical estimates of these two properties and demonstrate they depend upon a dimensionless pumping rate, denoted xi. The bromide breakthrough curve predicted from theory agrees well with that determined experimentally at Moffett Field. The minimum travel time between the wells is denoted t(min). In theory, t(min) depends inversely on Q, the pumping rate in the recirculating wells, and is proportional to a2, the square of the distance between the wells. Both the experimental and theoretical travel-time distributions indicate that at least half the recirculating water travels between the wells along fast flowpaths (travel time < 2*t(min)). Therefore, when designing recirculating well pairs, engineers should ensure that t(min) will be sufficiently high to allow biologically mediated reactions (or other in situ remediation processes) sufficient time to proceed.     

Correlations and sequence stratigraphic model for Messinian carbonate platforms of the western and central Mediterranean

Distance correlations of Late Tortonian–Messinian littoral carbonate complexes are proposed from the study of eight platforms in the western and central Mediterranean. Correlations are based on the identification of two major biological sedimentary cycles and of two index surfaces. Surface A is a maximum flooding surface during cycle 1 at around 6.7 Ma. Surface B is a regional marine planation surface at around 5.95 Ma, at the base of cycle 2 (Terminal Carbonate Complex). A general sedimentary model is proposed for the 7–5.6-Ma time-span. The boundary between cycles 1 and 2 is coincident with the onset of the Messinian Salinity Crisis, and appears to be related to major environmental–paleo-oceanographic changes in the Mediterranean, rather than to a major sea-level drop or to climatic change.     

Inheritance of early Archaean Pb-isotope variability from long-lived Hadean protocrust

Comparison of initial Pb-isotope signatures of several early Archaean (3.65-3.82 Ga) lithologies (orthogneisses and metasediments) and minerals (feldspar and galena) documents the existence of substantial isotopic heterogeneity in the early Archaean, particularly in the ²⁰⁷Pb/²⁰⁴Pb ratio. The magnitude of isotopic variability at 3.82-3.65 Ga requires source separation between 4.3 and 4.1 Ga, depending on the extent of U/Pb fractionation possible in the early Earth. The isotopic heterogeneity could reflect the coexistence of enriched and depleted mantle domains or the separation of a terrestrial protocrust with a ²³⁸U/²⁰⁴Pb (µ) that was ca. 20-30% higher than coeval mantle. We prefer this latter explanation because the high-µ signature is most evident in metasediments (that formed at the Earth's surface). This interpretation is strengthened by the fact that no straightforward mantle model can be constructed for these high-µ lithologies without violating bulk silicate Earth constraints. The Pb-isotope evidence for a long-lived protocrust complements similar Hf-isotope data from the Earth's oldest zircons, which also require an origin from an enriched (low Lu/Hf) environment. A model is developed in which ́.8-Ga tonalite and monzodiorite gneiss precursors (for one of which we provide zircon U-Pb data) are not mantle-derived but formed by remelting or differentiation of ancient (ca. 4.3 Ga) basaltic crust which had evolved with a higher U/Pb ratio than coeval mantle in the absence of the subduction process. With the initiation of terrestrial subduction at, we propose, ca. 3.75 Ga, most of the ́.8-Ga basaltic shell (and its differentiation products) was recycled into the mantle, because of the lack of a stabilising mantle lithosphere. We argue that the key event for preservation of all ́.8-Ga terrestrial crust was the intrusion of voluminous granitoids immediately after establishment of global subduction because of complementary creation of a lithospheric keel. Furthermore, we argue that preservation of ́.8-Ga material (in situ rocks and zircons) globally is restricted to cratons with a high U/Pb source character (North Atlantic, Slave, Zimbabwe, Yilgarn, and Wyoming), and that the Pb-isotope systematics of these provinces are ultimately explained by reworking of material that was derived from ca. 4.3 Ga (i.e. Hadean) basaltic crust.     

Pyrite oxidation inhibition by a cross-linked lipid coating

The effect of a diacetylene-containing phospholipid on the oxidation of pyrite, FeS₂, was investigated. Earlier work reported by our research group showed that the adsorption of l,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine on pyrite suppressed the extent of its oxidation by about 75% over a specific time period. Results presented here show that the pre-exposure to UV radiation of this lipid after sorption onto pyrite results in a 90% suppression. Attenuated total reflection (ATR) Fourier transform infra-red spectroscopy (FTIR) suggests that the UV irradiation of the lipid does not result in degradation of the adsorbed layer. It is believed that the UV exposure results in the cross-linking and polymerization of the adsorbed phospholipid into a relatively impermeable barrier that separates the pyrite from the aqueous phase. The results of this study might have implications for the protection of pyrite from oxidation in the environment.     

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park,Wyoming, USA. III. An anion-exchange resin technique for sampling and preservation of sulfoxyanions in natural waters

A sampling protocol for the retention, extraction, and analysis of sulfoxyanions in hydrothermal waters has been developed in the laboratory and tested at Yellowstone National Park and Green Lake, NY. Initial laboratory testing of the anion-exchange resin Bio-Rad™ AG1-X8 indicated that the resin was well suited for the sampling, preservation, and extraction of sulfate and thiosulfate. Synthetic solutions containing sulfate and thiosulfate were passed through AG1-X8 resin columns and eluted with 1 and 3 M KCl, respectively. Recovery ranged from 89 to 100%. Comparison of results for water samples collected from five pools in Yellowstone National Park between on-site IC analysis (U.S. Geological Survey mobile lab) and IC analysis of resin-stored sample at SUNY-Stony Brook indicates 96 to 100% agreement for three pools (Cinder, Cistern, and an unnamed pool near Cistern) and 76 and 63% agreement for two pools (Sulfur Dust and Frying Pan). Attempts to extract polythionates from the AG1-X8 resin were made using HCl solutions, but were unsuccessful. Bio-Rad™ AG2-X8, an anion-exchange resin with weaker binding sites than the AG1-X8 resin, is better suited for polythionate extraction. Sulfate and thiosulfate extraction with this resin has been accomplished with KCl solutions of 0.1 and 0.5 M, respectively. Trithionate and tetrathionate can be extracted with 4 M KCl. Higher polythionates can be extracted with 9 M hydrochloric acid. Polythionate concentrations can then be determined directly using ion chromatographic methods, and laboratory results indicate recovery of up to 90% for synthetic polythionate solutions using AG2-X8 resin columns.     

Upward-thickening patterns and lateral continuity of Permian sand-rich turbidite channel fills, Laingsburg Karoo, South Africa

Abstract Analysis of extensive exposures of the Permian Laingsburg Formation, Karoo basin, South Africa, have enabled a detailed reconstruction of the base of slope stratigraphy and palaeoenvironments in a deep-water system characterized by a very narrow grain-size range (fine sandstone). The deposits include an ≈ 4 km wide and 80 m thick channel complex, fringed by sandy sheet deposits that extend laterally for at least 6 km across depositional strike. Within the channel complex, individual channel fills are marked by shallow basal erosion surfaces draped by thin, parallel-stratified beds of very fine sandstone and siltstone, interpreted as flow tails to largely bypassing flows. These thin beds are overlain by 0·4 to 5 m thick beds of structureless, fine-grained sandstone that represent the majority of the channel fills. The basal packages may be partially to completely removed by localized scour in the axial zone of the channel complex but can be mapped laterally into overbank areas where they thicken and are dominated by rippled fine sandstones with intercalated siltstones. Axial confinement resulted from subtle topography on the basin floor, whereby the lower, dense parts of the initially erosive and bypassing flows were partially confined in the lows and the more dilute, slower moving upper parts of the flows deposited sheet-like successions across slightly elevated overbank areas. The narrow grain-size distribution prohibited the formation ofcoarse-grained residual bypass deposits during the initial phases of channel formation. With decreasing magnitude, later flows became more depositional, filling remaining axial depressions with thick-bedded structureless sandstone. The smaller volumes of late-stage sediment were more axially focused, producing local scour-and-fill features and starvation of the overbank areas. Resulting grain-size vertical profiles are complex. The basal flow tail packages and overlying massive deposits form a thickening and slightly coarsening-upward trend in the channel fills. The overbank deposits show a thinning- and fining-upward profile as a result of less bypass plus late-stage starvation of sand. Application of traditional deep-water facies models could therefore potentially lead to erroneous interpretations of the channel complex as a prograding lobe and the overbank sheets as channel-fills.     

Surface water/groundwater interaction in the Piora Aquifer,Switzerland: evidence from dye tracing tests

Results of seven dye tracing tests done from 1993–1997 to investigate the extent to which lakes and surface water interact with the underlying Triassic Piora Aquifer, Switzerland, are reported here. Two of the dye tracing tests showed that groundwater flows in the Piora Aquifer from the Piora Valley to springs in the adjacent Santa Maria Valley, and even further east to the di Campo Valley considerably outside of the Piora Valley surface water divide. Lake Ritom located in the Piora Valley loses water only to the Canaria Valley outside of the lake's surface-water watershed at the lake's western margin when lake levels are above 1,835 m above sea level. Dye tracing tests show that a major sinkhole in the Piora Valley, Calderoni Sinkhole, is located precisely on the water divide where subsurface flow in the Piora Valley and surface water diverge and move in opposite directions. The dye tracing results also showed no hydraulic connection between surface water in the Piora Valley and the famous Pertusio Spring, located in the upper Santa Maria Valley. Only a small amount of dye from the two dye tracing tests done in 1993 and 1997 entered an exploratory gallery built to test the viability of the AlpTransit tunnel, being built in competent rock under the Triassic Piora Aquifer, effectively perched above. Electronic Publication     

Geoid determination using one-step integration

A residual (high-frequency) gravimetric geoid is usually computed from geographically limited ground, sea and/or airborne gravimetric data. The mathematical model for its determination from ground gravity is based on the transformation of observed discrete values of gravity into gravity potential related to either the international ellipsoid or the geoid. The two reference surfaces are used depending on height information that accompanies ground gravity data: traditionally orthometric heights determined by geodetic levelling were used while GPS positioning nowadays allows for estimation of geodetic (ellipsoidal) heights. This transformation is usually performed in two steps: (1) observed values of gravity are downward continued to the ellipsoid or the geoid, and (2) gravity at the ellipsoid or the geoid is transformed into the corresponding potential. Each of these two steps represents the solution of one geodetic boundary-value problem of potential theory, namely the first and second or third problem. Thus two different geodetic boundary-value problems must be formulated and solved, which requires numerical evaluation of two surface integrals. In this contribution, a mathematical model in the form of a single Fredholm integral equation of the first kind is presented and numerically investigated. This model combines the solution of the first and second/third boundary-value problems and transforms ground gravity disturbances or anomalies into the harmonically downward continued disturbing potential at the ellipsoid or the geoid directly. Numerical tests show that the new approach offers an efficient and stable solution for the determination of the residual geoid from ground gravity data.