Setting nutrient thresholds to support an ecological assessment based on nutrient enrichment, potential primary production and undesirable disturbance

The EU Water Framework Directive recognises that ecological status is supported by the prevailing physico-chemical conditions in each water body. This paper describes an approach to providing guidance on setting thresholds for nutrients taking account of the biological response to nutrient enrichment evident in different types of water. Indices of pressure, state and impact are used to achieve a robust nutrient (nitrogen) threshold by considering each individual index relative to a defined standard, scale or threshold. These indices include winter nitrogen concentrations relative to a predetermined reference value; the potential of the waterbody to support phytoplankton growth (estimated as primary production); and detection of an undesirable disturbance (measured as dissolved oxygen). Proposed reference values are based on a combination of historical records, offshore (limited human influence) nutrient concentrations, literature values and modelled data. Statistical confidence is based on a number of attributes, including distance of confidence limits away from a reference threshold and how well the model is populated with real data. This evidence based approach ensures that nutrient thresholds are based on knowledge of real and measurable biological responses in transitional and coastal waters.     

The Taihua group on the southern margin of the North China craton: further insights from U–Pb ages and Hf isotope compositions of zircons

The "Taihua Group" is a collective term for a series of old terranes scattered along the southern margin of the North China Craton. The timing of formation and thermal overprinting of the Taihua Group have long been contentious, and its relationship with the Qinling orogenic belt has been unclear. In this study, new data from integrated in-situ U–Pb dating and Hf isotope analysis of zircons from an amphibolite (from the Xiong’ershan terrane) and a biotite gneiss (from the Lantian-Xiaoqinling terrane) indicate that the Upper Taihua Group formed during the Paleoproterozoic (2.3–2.5 Ga) and thus was originally part of the southern edge of North China Craton, detached during the Mesozoic Qinling orogeny and displaced about 100 km north from its original location. This suggests that the Taihua Group became part of the tectonic terrane associated with the Qinling orogeny and now forms part of the overthrust basement section of the Qinling belt. Before the Qinling orogeny, the Taihua Group was metamorphosed at 2.1 Ga. The initial Hf-isotope compositions of zircons, together with positive εNd(t) values for the whole-rocks, imply that the original magmas were derived from a juvenile source with some assimilation of an Archean crustal component.     

Modeling bio-geomorphological influences for offshore sandwaves

The coastal environment shows a wide range of bed patterns, for which sandwaves and sandbanks are among the most common. Less known in this context is the high benthic diversity in the coastal environment, which gives rise to the question to what extend the benthos interacts with the shape of the seabed. This paper reviews field and flume experiments on bio-geomorphological influences between benthos and sediment and tests the hypothesis that both the occurrence and the dimensions of sandwaves are dependent on the benthic diversity in the North Sea. Mathematical inclusions to account for biological activity in idealized models reveal that biota is able to influence the wavelength of sandwaves significantly, compared to the default case. More importantly, the models indicate that biota is able to induce bed patterns under conditions when the physical parameters suggest a stable flat bed and vice versa. Present model explorations indicate that future research should focus on the parameterization of subtidal biological activity on sediment dynamics and thereby on seabed patterns. Such knowledge will enable process-based modeling of the spatial and temporal variation in biological activity on seabed morphodynamics and validate the proposed modeling approach with field measurements.     

Mineral inclusions and geochemical characteristics of microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, Canada

A mineral inclusion, carbon isotope, nitrogen content, nitrogen aggregation state and morphological study of 576 microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, was conducted. Mineral inclusion data show the diamonds are largely eclogitic (64%), followed by peridotitic (25%) and ultradeep (11%). The paragenetic abundances are similar to macrodiamonds from the DO27 kimberlite (Davies, R.M., Griffin, W.L., O'Reilly, S.Y., 1999. Diamonds from the deep: pipe DO27, Slave craton, Canada. In: Gurney, J.J., Gurney, J.L., Pascoe, M.D., Richardson, S.H. (Eds.), The J. B. Dawson Vol., Proc. 7th Internat. Kimberlite Conf., Red Roof Designs, Cape Town, pp. 148–155) but differ to diamonds from nearby kimberlites at Ekati (e.g., Lithos (2004); Tappert, R., Stachel, T., Harris, J.W., Brey, G.P., 2004. Mineral Inclusions in Diamonds from the Panda Kimberlite, S. P., Canada. 8th International Kimberlite Conference, extended abstracts) and Snap Lake to the south (Dokl. Earth Sci. 380 (7) (2001) 806), that are dominated by peridotitic stones.

Eclogitic diamonds with variable inclusion compositions and temperatures of formation (1040–1300 °C) crystallised at variable lithospheric depths sometimes in changing chemical environments. A large range to very ¹³C-depleted C-isotope compositions (δ¹³C=−35.8‰ to −2.2‰) and an NMORB bulk composition, calculated from trace elements in garnet and clinopyroxene inclusions, are consistent with an origin from subducted oceanic crust and sediments. Carbon isotopes in the peridotitic diamonds have mantle compositions (δ¹³C mode −4.0‰). Mineral inclusion compositions are largely harzburgitic. Variable temperatures of formation (garnet T_Ni=800–1300 °C) suggest the peridotitic diamonds originate from the shallow ultra-depleted and deeper less depleted layers of the central Slave lithosphere. Carbon isotopes (δ¹³C av.=−5.1‰) and mineral inclusions in the ultradeep diamonds suggest they formed in peridotitic mantle (670 km). The diamonds may have been entrained in a plume and subcreted to the base of the central Slave lithosphere.

Poorly aggregated nitrogen (IaA without platelets) in a large number of eclogitic (67%) and peridotitic (32%) diamonds, with similar nitrogen contents, indicates the diamonds were stored in the mantle at low temperatures (1060–<1100 °C) following crystallisation in the Archean. Type IaA diamonds have largely cubo-octahedral growth forms, and Type II and Type IaAB diamonds, with higher nitrogen aggregation states, mostly have octahedral morphologies. However, no correlation between these groups and their mineral inclusion compositions, C-isotopes, and N-contents rules out the possibility of unique source origins and suggests eclogitic and peridotitic diamonds experienced variable mantle thermal states. Variation in mineral inclusion chemistries in single diamonds, possible overgrowths of ¹³C-depleted eclogitic diamond on diamonds with peridotitic and ultradeep inclusions, and Type I ultradeep diamond with low N-aggregation is consistent with diamond growth over time in changing chemical environments.     

Arsenic in an alkaline AMD treatment sludge: Characterization and stability under prolonged anoxic conditions

Lime treatment of acid mine drainage (AMD) generates large volumes of neutralization sludge that are often stored under water covers. The sludge consists mainly of calcite, gypsum and a widespread ferrihydrite-like Fe phase with several associated species of metal(loid) contaminants. The long-term stability of metal(loid)s in this chemically ill-defined material remains unknown. In this study, the stability and speciation of As in AMD sludge subjected to prolonged anoxic conditions is determined. The total As concentration in the sludge is 300 mg kg⁻¹. In the laboratory, three distinct water cover treatments were imposed on the sludge to induce different redox conditions (100%N₂, 100%N₂ + glucose, 95%N₂:5%H₂). These treatments were compared against a control of oxidized, water-saturated sludge. Electron micro-probe (EMP) analysis and spatially resolved synchrotron X-ray fluorescence (SXRF) results indicate that As is dominantly associated with Fe in the sludge. In all treatments and throughout the experiment, measured concentrations of dissolved As were less than 5 μg L⁻¹. Dissolved Mn concentration in the N₂ + glucose treatment increased significantly compared to other treatments. Manganese and As K-edge X-ray absorption near edge structure spectroscopy (XANES) analyses showed that Mn was the redox-active element in the solid-phase, while As was stable. Arsenic(V) was still the dominant species in all water-covered sludges after 9 months of anoxic treatments. In contrast, Mn(IV) in the original sludge was partially reduced into Mn(II) in all water-covered sludges. The effect was most pronounced in the N₂ + glucose treatment, suggesting microbial reduction. Micro-scale SXRF and XANES analysis of the treated sludge showed that Mn(II) accumulated in areas already enriched in Fe and As. Overall, the study shows that AMD sludges remain stable under prolonged anoxic conditions. External sources of chemical reductants or soluble C were needed to induce lower redox state in the systems, and even under these imposed treatments, only weakly reducing conditions (Mn threshold) developed. The results suggest that As(V) in AMD sludge will remain stable under prolonged anoxic conditions as long as Mn(IV) is present and organic matter accumulation is negligible.     

U–Pb and Hf-isotope analysis of zircons in mafic xenoliths from Fuxian kimberlites: evolution of the lower crust beneath the North China craton

Mafic xenoliths from the Paleozoic Fuxian kimberlites in the North China craton include garnet granulite, and minor pyroxene amphibolite, metagabbro, anorthosite and pyroxenite. The formation conditions of the amphibolites are estimated at 745–820 °C and 7.6–8.8 Kb (25–30 km); the granulites probably are derived from greater depths in the lower crust. LAM-ICPMS U–Pb dating of zircons from four granulites reveals multiple age populations, recording episodes of magmatic intrusion and metamorphic recrystallisation. Concordant ages and upper intercept ages, interpreted as minimum estimates for the time of magmatic crystallisation, range from 2,620 to 2,430 Ma in three granulites, two amphibolites and two metagabbros. Lower intercept ages, represented by near-concordant zircons, are interpreted as reflecting metamorphic recrystallisation, and range from 1,927 to 1,852 Ma. One granulite contains two metamorphic zircon populations, dated at 1,927±55 Ma and 600–700 Ma. Separated minerals from one granulite and one amphibolite yield Sm–Nd isochron ages of 1,619±48 Ma (¹⁴³Nd/¹⁴⁴Nd)i=0.51078), and 1,716±120 Ma (¹⁴³Nd/¹⁴⁴Nd)i=0.51006), respectively. These ages are interpreted as recording cooling following metamorphic resetting; model ages for both samples are in the range 2.40–2.66 Ga. LAM-MC-ICPMS analyses of zircon show a range in ¹⁷⁶Hf/¹⁷⁷Hf from 0.28116 to 0.28214, corresponding to a range of _Hf from –34 to +12. The relationships between ²⁰⁷Pb/²⁰⁶Pb age and _Hf show that: (1) the granulites, amphibolites and metagabbro were derived from a depleted mantle source at 2.6–2.75 Ga; (2) zircons in most samples underwent recrystallisation and Pb loss for 100–200 Ma after magmatic crystallisation, consistent with a residence in the lower crust; (3) metamorphic zircons in several samples represent new zircon growth, incorporating Hf liberated from breakdown of silicates with high Lu/Hf; (4) in other samples metamorphic and magmatic zircons have identical ¹⁷⁶Hf/¹⁷⁷Hf, and the younger ages reflect complete resetting of U–Pb systems in older zircons. The Fuxian mafic xenoliths are interpreted as the products of basaltic underplating, derived from a depleted mantle source in Neoarchean time, an important period of continental growth in the North China craton. Paleoproterozoic metamorphic ages indicate an important tectonic thermal event in the lower crust at 1.8–1.9 Ga, corresponding to the timing of collision between the Eastern and Western Blocks that led to the final assembly of the North China craton. The growth of metamorphic zircon at 600–700 Ma may record an asthenospheric upwelling in Neoproterozoic time, related to uplift and a regional disconformity in the North China craton.     

Exploring weathering and regolith transport controls on Critical Zone development with models and natural experiments

The architecture of the Critical Zone, including mobile regolith thickness and depth to the weathering front, is first order controlled by advance of a weathering front at depth and transport of sediment at the surface. Differences in conditions imposed by slope aspect in the Gordon Gulch catchment of the Boulder Creek Critical Zone Observatory present a natural experiment to explore these interactions. The weathering front is deeper and saprolite more decayed on north-facing than on south-facing slopes. Simple numerical models of weathering front advance, mobile regolith production, and regolith transport are used to test how weathering and erosion rates interact in the evolution of weathered profiles. As the processes which attempt are being made to mimic are directly tied to climate variables such as mean annual temperature, the role of Quaternary climate variation in governing the evolution of Critical Zone architecture can be explored with greater confidence.     

Preserved organic matter in a fossil Ocean Continent Transition in the Alps: the example of Totalp,SE Switzerland

Evidence from ultraslow spreading mid-ocean ridges and both fossil and present-day Ocean–Continent Transitions (OCT) demonstrates that mantle serpentinization resulting from the interaction of mantle rock and water during tectonic exhumation is widespread. Observations at white smokers in modern ocean settings suggest that methane produced by serpentinization can support methanotrophic bio-systems, which use methane as the only source of carbon. An important question is whether such bio-systems are more generally pervasive in their association with serpentinized mantle in the subsurface. In this study, we examined whether there is evidence for such a methanotrophic system in exhumed serpentinized mantle at a magma-poor rifted continental margin, by probing for characteristic biological markers in these and associated sedimentary rocks in the Totalp unit of SE Switzerland. This unit represents a remnant of the former OCT of the southern Alpine Tethyan margin and was chosen because of its mild Alpine tectonic and low-grade metamorphic overprint during Alpine orogeny, hence giving potential for the preservation of indigenous organic matter (OM). Totalp samples are characterized by low organic carbon contents of 11–647 ppm. The majority of the samples contain hydrocarbons in the form of n-alkanes in the range C₁₇–C₃₆. Some sediments contain isoprenoids, for example pristane and phytane and a suite of steranes that are consistent with a marine origin for the OM preserved in the rocks. Traces of marine planktonic and bacterial OM are preserved in the serpentinized mantle and overlying sediments of this ancient Tethyan OCT, but there is no evidence that the OM has been generated from methanotrophic bio-systems.     

Carbonatite metasomatized peridotite xenoliths from southern Patagonia: implications for lithospheric processes and Neogene plateau magmatism

The mineral chemistry, major and trace element, and Sr–Nd isotopic composition of Cr-diopside, spinel peridotite xenoliths from the Estancia Lote 17 locality in southern Patagonia document a strong carbonatitic metasomatism of the backarc continental lithosphere. The Lote 17 peridotite xenolith suite consists of hydrous spinel lherzolite, wehrlite, and olivine websterite, and anhydrous harzburgite and lherzolite. Two-pyroxene thermometry indicates equilibration temperatures ranging from 870 to 1015 °C and the lack of plagioclase or garnet suggests the xenoliths originated from between ˜40 and 60 km depth. All of the xenoliths are LILE- and LREE-enriched, but have relatively low ⁸⁷Sr/⁸⁶Sr (0.70294 to 0.70342) and high ɛ_Nd (+3.0 to +6.6), indicating recent trace element enrichment (∼25 Ma, based on the low ⁸⁷Sr/⁸⁶Sr and high Rb concentrations of phlogopite separates) in the long-term, melt-depleted Patagonian lithosphere. Lote 17 peridotite xenoliths are divided into two basic groups. Group 1 xenoliths consist of fertile peridotites that contain hydrous phases (amphibole ± phlogopite ± apatite). Group 1 xenoliths are further subdivided into three groups (a, b, and c) based on distinctive textures and whole-rock chemistry. Group 1 xenolith mineralogy and chemistry are consistent with a complex metasomatic history involving variable extents of recent carbonatite metasomatism (high Ca/Al, Nb/La, Zr/Hf, low Ti/Eu) that has overprinted earlier metasomatic events. Group 2 xenoliths consist of infertile, anhydrous harzburgites and record cryptic metasomatism that is attributed to CO₂-rich fluids liberated from Group 1 carbonatite metasomatic reactions. Extremely variable incompatible trace element ratios and depleted Sr–Nd isotopic compositions of Lote 17 peridotite xenoliths indicate that the continental lithosphere was neither the primary source nor an enriched lithospheric contaminant for Neogene Patagonian plateau lavas. Neogene plateau magmatism associated with formation of asthenospheric slab windows may have triggered this occurrence of “intraplate-type” carbonatite metasomatism in an active continental backarc setting. Received: 26 January 2000 / Accepted: 1 March 2000