Natural and Post-Urbanization Signatures of Hypoxia in Two Basins of Puget Sound: Historical Reconstruction of Redox Sensitive Metals and Organic Matter Inputs

Hypoxia has been observed in Hood Canal, Puget Sound, WA, USA since the 1970s. Four long sediment cores were collected in 2005 and age-dated to resolve natural and post-urbanization signatures of hypoxia and organic matter (OM) sources in two contrasting basins of Puget Sound: Main Basin and Hood Canal. Paleoecological indicators used for sediment reconstructions included pollen, stable carbon and nitrogen isotopes (??¹³C and ??¹⁵N), biomarkers of terrestrial OM (TOM), biogenic silica (BSi), and redox-sensitive metals (RSM). The sedimentary reconstructions illustrated a gradient in RSM enrichment factors as Hood Canal > Main Basin, southern > northern cores, and pre-1900s > 1900?C2005. The urbanization of Puget Sound watersheds during the 1900s was reflected as shifts in all the paleoecological signatures. Pollen distributions shifted from predominantly old growth conifer to successional alder, dominant OM signatures recorded a decrease in the proportion of marine OM (MOM) concomitant with an increase in the proportion of TOM, and the weight % of BSi decreased. However, these shifts were not coincidental with an overall increase in the enrichment of RSM or ??¹⁵N signatures indicative of cultural eutrophication. The increased percentage of TOM was independently verified by both the elemental ratios and lignin yields. In addition, isotopic signatures, BSi, and RSMs all suggest that OM shifts may be due to a reduction in primary productivity rather than an increase in OM regeneration in the water column or at the sediment/water interface. Therefore, the reconstructions suggested the Hood Canal has been under a more oxygenated ??stance?? during the twentieth century compared to prior periods. However, these 2005 cores and their resolutions do not encompass the period of high resolution water column measurements that showed short-lived hypoxia events and fish kills in Hood Canal during the early twenty-first century. The decoupling between the increased watershed-scale anthropogenic alterations recorded in the OM signatures and the relatively depleted RSM during the twentieth century suggests that physical processes, such as deep-water ventilation, may be responsible for the historical variation in oxygen levels. Specifically, climate oscillations may influence the ventilation and/or productivity of deep water in Puget Sound and particularly their least mixed regions.     

Stately home geology: Kelmscott Manor,Oxfordshire, UK

Kelmscott Manor on the banks of the Upper Thames in Oxfordshire is a place of pilgrimage for social historians and conversationalists as well as those who simply want to turn the clock back to a rural England long departed. The manor was leased to William Morris in 1871 to be his family home until long after his death in 1896—their escape from the hectic daily life in London. At that point, Morris spent the previous 10 years building up the crafts business for which he is best known, the patterned textiles and wallpaper designs and the basic wooden furniture we associate with the Arts and Crafts Movement. It can be difficult to remember that much of the respected craftwork was generated in the East End of London by gifted craftsmen.     

Age and paleoclimatic significance of late Holocene lakes in the Carson Sink, NV, USA

New dating in the Carson Sink at the termini of the Humboldt and Carson rivers in the Great Basin of the western United States indicates that lakes reached elevations of 1204 and 1198 m between 915 and 652 and between 1519 and 1308 cal yr B.P., respectively. These dates confirm Morrison's original interpretation (Lake Lahontan: Geology of the Southern Carson Desert, Professional Paper 40, U.S. Geol. Survey, 1964) that these shorelines are late Holocene features, rather than late Pleistocene as interpreted by later researchers. Paleohydrologic modeling suggests that discharge into the Carson Sink must have been increased by a factor of about four, and maintained for decades, to account for the 1204-m lake stand. The hydrologic effects of diversions of the Walker River to the Carson Sink were probably not sufficient, by themselves, to account for the late Holocene lake-level rises. The decadal-long period of increased runoff represented by the 1204-m lake is also reflected in other lake records and in tree ring records from the western United States.     

Depositional environment of a Kimmeridgian carbonate 'black band' (Akkuyu Formation, south-western Turkey)

The Upper Jurassic Akkuyu Formation of south-western Turkey consists of pale-coloured carbonate facies, but includes a peculiar ‘black band’ at its base. In order to characterize the depositional environment of this level, a sedimentological, organic and inorganic geochemical study was performed on 30 samples. Three units are distinguished. Unit 1 consists of black marlstones, very rich in organic carbon (22–30%) with HI (hydrogen index) values around 600. The organic matter is an amorphous homogeneous material even at nanoscopic scale. This unit is also characterized by a very high concentration of V ( >1000 p.p.m.) and a δ¹³C_org value around ?26·5‰. Unit 2 shows thin-bedded black limestones with chert layers. Its organic content varies from 2% to 6%. As in unit 1, the HI values are uniformly high (600), and gas chromatography shows a high quantity of hopanes. The V concentration is also high (≈400 p.p.m.). The unit has a high Sr/Ca ratio, an organic carbon isotopic ratio close to ?28·7‰ and diffuse, nanoscopically amorphous organic material that is closely associated with pyrite. Unit 3 corresponds to the white limestones overlying the ‘black band’. This calcitic facies is almost devoid of organic carbon (<0·1%). The δ¹³C_org values are similar to those of unit 1 (?25·5‰ to ?26‰). Deposition occurred in a basinal environment surrounded by a carbonate platform. Primary productivity was high but not exceptional; terrestrial organic inputs were scarce. Bottom waters were probably euxinic during the deposition of unit 1. The presence of both hopane-rich and sulphur-rich nanoscopically amorphous organic matter may be the result of strong sulphate-reducing bacterial activity. Coupled with low amounts of iron, this led to intense vulcanization of the organic matter and thus good preservation. With the onset of unit 2 deposition, environmental conditions became less extreme, perhaps because of cooler water temperatures. Finally, the depositional conditions became oxic, leading to the accumulation of pale-coloured organic-poor limestones of unit 3.     

The removal kinetics of dissolved organic matter and the optical clarity of groundwater

Concentrations of dissolved organic matter (DOM) and ultraviolet/visible light absorbance decrease systematically as groundwater moves through the unsaturated zones overlying aquifers and along flowpaths within aquifers. These changes occur over distances of tens of meters (m) implying rapid removal kinetics of the chromophoric DOM that imparts color to groundwater. A one-compartment input-output model was used to derive a differential equation describing the removal of DOM from the dissolved phase due to the combined effects of biodegradation and sorption. The general solution to the equation was parameterized using a 2-year record of dissolved organic carbon (DOC) concentration changes in groundwater at a long-term observation well. Estimated rates of DOC loss were rapid and ranged from 0.093 to 0.21 micromoles per liter per day (μM d^?1), and rate constants for DOC removal ranged from 0.0021 to 0.011 per day (d^?1). Applying these removal rate constants to an advective-dispersion model illustrates substantial depletion of DOC over flow-path distances of 200 m or less and in timeframes of 2 years or less. These results explain the low to moderate DOC concentrations (20–75 μM; 0.26–1 mg L^?1) and ultraviolet absorption coefficient values (a ₂₅₄?<?5 m^?1) observed in groundwater produced from 59 wells tapping eight different aquifer systems of the United States. The nearly uniform optical clarity of groundwater, therefore, results from similarly rapid DOM-removal kinetics exhibited by geologically and hydrologically dissimilar aquifers.     

Chemical evolution of the Mt. Hekla,Iceland, groundwaters: A natural analogue for CO2 sequestration in basaltic rocks

A detailed study of the chemical composition of the groundwater surrounding the Mt. Hekla volcano in south Iceland was performed to assess fluid evolution and toxic metal mobility during CO₂-rich fluid basalt interaction. These fluids provide a natural analogue for evaluating the consequences of CO₂ sequestration in basalt. The concentration of dissolved inorganic C in these groundwaters decreases from 3.88 to 0.746 mmol/kg with increasing basalt dissolution while the pH increases from 6.9 to 9.2. This observation provides direct evidence of the potential for basalt dissolution to sequester CO₂. Reaction path calculations suggest that dolomite and calcite precipitation is largely responsible for this drop in groundwater dissolved C concentration. The concentrations of toxic metal(loid)s in the waters are low, for example the maximum measured concentrations of Cd, As and Pb were 0.09, 22.8 and 0.06 nmol/kg, respectively. Reaction path modelling indicates that although many toxic metals may be initially liberated by the dissolution of basalt by acidic CO₂-rich solutions, these metals are reincorporated into solid phases as the groundwaters are neutralized by continued basalt dissolution. The identity of the secondary toxic metal bearing phases depends on the metal. For example, calculations suggest that Sr and Ba are incorporated into carbonates, while Pb, Zn and Cd are incorporated into Fe (oxy)hydroxide phases.     

Establishing constraints on groundwater ages with Cl,C, H,and noble gases: A case study in the eastern Paris basin,France

Groundwaters from the Tithonian/Kimmeridgian, Oxfordian and Upper Dogger aquifers, within the eastern part of the Paris basin (France), were characterised using ³H, ¹⁴C and ³⁶Cl, and noble gases tracers, to evaluate their residence times and determine their recharge period. This information is an important prerequisite to evaluating the confinement properties of the Callovo-Oxfordian clay formation sandwiched between the Oxfordian aquifer and the Dogger aquifer, currently being investigated by the French nuclear waste management agency (Andra) for radioactive waste disposal. Data presented in this paper are used to test 4 hypotheses.     

Constraint energy minimizing generalized multiscale finite element method in the mixed formulation

This paper presents a novel mass-conservative mixed multiscale method for solving flow equations in heterogeneous porous media. The media properties (the permeability) contain multiple scales and high contrast. The proposed method solves the flow equation in a mixed formulation on a coarse grid by constructing multiscale basis functions. The resulting velocity field is mass-conservative on the fine grid. Our main goal is to obtain first-order convergence in terms of the mesh size which is independent of local contrast. This is achieved, first, by constructing some auxiliary spaces, which contain global information that cannot be localized, in general. This is built on our previous work on the generalized multiscale finite element method (GMsFEM). In the auxiliary space, multiscale basis functions corresponding to small (contrast-dependent) eigenvalues are selected. These basis functions represent the high-conductivity channels (which connect the boundaries of a coarse block). Next, we solve local problems to construct multiscale basis functions for the velocity field. These local problems are formulated in the oversampled domain, taking into account some constraints with respect to auxiliary spaces. The latter allows fast spatial decay of local solutions and, thus, allows taking smaller oversampled regions. The number of basis functions depends on small eigenvalues of the local spectral problems. Moreover, multiscale pressure basis functions are needed in constructing the velocity space. Our multiscale spaces have a minimal dimension, which is needed to avoid contrast dependence in the convergence. The method’s convergence requires an oversampling of several layers. We present an analysis of our approach. Our numerical results confirm that the convergence rate is first order with respect to the mesh size and independent of the contrast.     

Transition from arid to hyper-arid environment in the southern Levant deserts as recorded by early Pleistocene cummulic Aridisols

The time at which deserts established their current arid or hyper-arid conditions remains a fundamental question regarding the history of Earth. Cosmogenic isotope exposure ages of desert pavement and welded, calcic–gypsic–salic Reg soils that developed on relatively flat alluvial surfaces ～2 Ma ago in the Negev Desert indicate long geomorphic stability under extremely dry conditions. Over a short interval during their initial stage of development between 1–2 Ma, these cumulative soils are characterized by calcic soils reaching maximum stage III of carbonate morphology. This interval is the only period when calcic soil horizons formed on stable abandoned alluvial surfaces in the southern Negev Desert. Since ～1 Ma pedogenesis changed toward more arid soil environment and the formation of gypsic–salic soil horizons that were later followed by dust accumulation. The dichotomy of only moderately-developed calcic soil (stages II–III) during a relatively long time interval (10⁵–10⁶ years) indicates an arid environment that does not support continuous development but only occasional calcic soil formation. The very low δ¹⁸O and relatively high δ¹³C values of these early pedogenic carbonates support soil formation under arid climatic conditions. Such an environment was probably characterized by rare and relatively longer duration rainstorms which occasionally allowed deeper infiltration of rainwater and longer retention of soil moisture. This, in turn enabled the growth of sparse vegetation that enhanced deposition of pedogenic carbonate. At ～1 Ma these rare events of slightly wetter conditions ceased and less atmospheric moisture reached the southern Negev Desert leading to deposition of soluble salts and dust deposited in the soils. The combination of long-term hyperaridity, scarcity of vegetation and lack of bioturbation, salts cementation, dust accumulation and tight desert pavement cover, has protected the surfaces from erosion forming one of the most remarkably stable landscapes on Earth, a landscape that essentially has not eroded, but accumulated salt and dust for more than 10⁶ yr.