Assessing the response of watersheds to catastrophic (logging) and possible secular (global temperature change) perturbations using sediment-chemical chronologies

Geochemical profiles of sediment cores from two oligotrophic lakes (Elk and Mullett) in northern Lower Michigan were studied to examine the response and recovery of watersheds to large-scale logging that occurred between 1850 and 1920. Specific questions addressed were: can the impact of extensive clear-cutting of forests be recognized in the sediment-chemical chronologies, can states of system stability be identified prior to the logging, and are there indications that the systems are recovering and possibly returning to a stable state? To answer these questions, elements were put into four groups as proxies for watershed runoff or export (e.g., Al, Mg), pollution (e.g., Pb, Cu), redox (e.g., Fe, As), and productivity (e.g., Ca, P). It was observed that vertical patterns of all proxies were influenced by logging and the early increases in concentration of pollution proxies were due to increased watershed export, not pollution. System stability might be recognized by relatively symmetrical vertical patterns among all of the proxies or secular changes of slowly increasing or decreasing vertical concentration trajectories. Some pre-logging trajectories were punctuated by episodes of slightly elevated concentrations that appear to be related to comparatively warmer periods during the Little Ice Age. Iron and Mn enrichments caused by increased watershed runoff might be misinterpreted as paleo-redox horizons. Results are interpreted to indicate that (1) reference conditions may be better defined as the temporal trends among proxy groups and not individual concentrations, (2) simply assuming pre-1800 conditions as a reference may not be appropriate, (3) inter-proxy group comparisons are needed to help for interpretations of intra-proxy group patterns, (4) the possible regime shift identified here might be expected for other ecosystems because of the intensity of human disturbances and secular changes, and (5) without consideration of a possible regime shift, recovery from logging is estimated to be on the order of 75–130 a, but shorter if regime shifts are considered.     

Multi-zone fusion crust formation and classification of the 2004 Auckland meteorite (L6, S5, and W0)

On June 12, 2004, a meteorite passed through Earth's atmosphere and landed under the television in the living room of a house in Auckland, New Zealand. Textural characteristics, the chemistry of olivine (Fa_23–24) and orthopyroxene (Fs_20.7), and the bulk rock triple oxygen isotopes (δ¹⁷O + 3.1; δ¹⁸O + 4.2‰) from the interior of the completely unweathered (W0) 1.3 kg meteorite, hereafter referred to as Auckland, suggest it to be a strongly metamorphosed fragment from the interior of a low iron ordinary chondrite (L6) parent asteroid. The occurrence of maskelynite but shock fracturing of olivine and pyroxene indicates Auckland experienced extreme shock metamorphism (S5), likely during Ordovician fragmentation of the asteroid parent. The fusion crust consists of three zones: (1) an innermost zone containing narrow Fe-Ni-S-bearing veins that migrated along pre-existing shock fractures in olivine and pyroxene; (2) a middle zone in which the meteorite partially melted to form a silicate glass and immiscible blebs of metal and troilite, and is accompanied by unmelted silicate minerals; and (3) an approximately 0.1 mm wide vesicular-rich outermost layer that largely melted, volatilizing sulfides, before quenching to form glass and olivine. Oxygen isotope values of the bulk rock and/or maskelynite of melted rim and modified substrate are 2–3‰ greater than the meteorite interior and indicate that up to 19% of terrestrial atmospheric O₂ was incorporated into the fusion crust during the formation. The fusion crust migrated inwards as ablation occurred, enabling melting, migration, and re-precipitation ± loss of sulfide and metal components, with the prominent glassy rim therefore forming from an already chemically modified zone.     

Estimating present day extreme water level exceedance probabilities around the coastline of Australia: tropical cyclone-induced storm surges

The incidence of major storm surges in the last decade have dramatically emphasized the immense destructive capabilities of extreme water level events, particularly when driven by severe tropical cyclones. Given this risk, it is vitally important that the exceedance probabilities of extreme water levels are accurately evaluated to inform risk-based flood and erosion management, engineering and for future land-use planning and to ensure the risk of catastrophic structural failures due to under-design or expensive wastes due to over-design are minimised. Australia has a long history of coastal flooding from tropical cyclones. Using a novel integration of two modeling techniques, this paper provides the first estimates of present day extreme water level exceedance probabilities around the whole coastline of Australia, and the first estimates that combine the influence of astronomical tides, storm surges generated by both extra-tropical and tropical cyclones, and seasonal and inter-annual variations in mean sea level. Initially, an analysis of tide gauge records has been used to assess the characteristics of tropical cyclone-induced surges around Australia. However, given the dearth (temporal and spatial) of information around much of the coastline, and therefore the inability of these gauge records to adequately describe the regional climatology, an observationally based stochastic tropical cyclone model has been developed to synthetically extend the tropical cyclone record to 10,000 years. Wind and pressure fields derived for these synthetically generated events have then been used to drive a hydrodynamic model of the Australian continental shelf region with annual maximum water levels extracted to estimate exceedance probabilities around the coastline. To validate this methodology, selected historic storm surge events have been simulated and resultant storm surges compared with gauge records. Tropical cyclone induced exceedance probabilities have been combined with estimates derived from a 61-year water level hindcast described in a companion paper to give a single estimate of present day extreme water level probabilities around the whole coastline of Australia. Results of this work are freely available to coastal engineers, managers and researchers via a web-based tool (www.sealevelrise.info). The described methodology could be applied to other regions of the world, like the US east coast, that are subject to both extra-tropical and tropical cyclones.     

A temperature-induced reversible transformation between paratacamite and herbertsmithite

The crystal chemistry of paratacamite has been re-evaluated by studying a crystal from the holotype specimen BM86958 of composition Cu_3.71Zn_0.29(OH)₆Cl₂ using single-crystal X-ray diffraction at 100, 200, 300, 353, 393 and 423 K. At 300 K paratacamite has space group $R\bar{3}$ with unit-cell parameters a 13.644 and c 14.035 Å and exhibits a pronounced subcell, a′ = ½a and c′ = c, analogous to that of the closely related mineral herbertsmithite, Cu₃Zn(OH)₆Cl₂. Between 353 and 393 K, paratacamite undergoes a reversible phase transformation to the herbertsmithite-like substructure, space group $R\bar{3}m$ , unit-cell parameters a 6.839 and c 14.072 Å (393 K). The transformation is characterised by a gradual reduction in intensity of superlattice reflections, which are absent at 393 and 443 K. On cooling from 443 to 300 K at ~10 K min^?1, the superlattice reflections reappear and the refined structures ( $R\bar{3}$ ) of the initial and recovered 300 K states are almost identical. The complete reversibility of the transformation establishes that paratacamite of composition Cu_3.71Zn_0.29(OH)₆Cl₂ is thermodynamically stable at ambient temperatures. The nature of the rhombic distortion of the M(2)O₆ octahedron is discussed by considering two possibilities that are dependent upon the nature of cation substitution in the interlayer sites.     

Improving Risk-Based Screening at Vapor Intrusion Sites in California

The attenuation factor (AF) of 0.03 recommended by the U.S. Environmental Protection Agency (USEPA) is increasingly being used by regulatory agencies for the development of subsurface vapor screening levels for vapor intrusion (VI). There are concerns, however, over the database used to derive the AF and the AF's applicability to building types and geographies not included in USEPA database. To derive a more technically defensible AF for subsurface vapor screening in California, a database consisting of 8415 paired indoor and subsurface vapor samples collected from 485 buildings at 36 sites in California was compiled. Filtering was applied to remove data of suspect quality that were potentially affected by background (non-VI) sources. Filtering reduced the size of the database to 788 indoor air and subsurface vapor pairs, 80% of which were trichloroethylene (TCE) measurements. An AF of 0.0008 was derived from only TCE vapor data, based on the ability of the AF to reliably identify buildings with indoor air concentrations above screening levels in 95% of cases where subsurface vapor screening levels were exceeded. The AF derived from this study demonstrated limited sensitivity to the variables typically considered important in VI characterization, which was partially attributed to relatively weak correlation of indoor air and subsurface vapor concentration data. The results of this study can be used to improve VI screening in California and other states and help focus limited resources on sites posing the greatest potential risk.     

The “Zero-order Model” revisited: Paul Schindler's influence on the development of trace metal scavenging models

In 1975 Paul Schindler produced the first oceanic trace metal scavenging model to explicitly include the role of surface chemistry as a control on trace metal water column residence times. The eighteen years that have elapsed since the publication of Schindler's seminal paper have seen the development of a variety of oceanic scavenging models; yet, the fundamental insight of his Zero-order Model remains the benchmark. This paper describes the role of Paul Schindler's work on surface chemistry in providing a framework for the current generation of trace element scavenging models.     

Revised 14C dating of ice wedge growth in interior Alaska (USA) to MIS 2 reveals cold paleoclimate and carbon recycling in ancient permafrost terrain

Establishing firm radiocarbon chronologies for Quaternary permafrost sequences remains a challenge because of the persistence of old carbon in younger deposits. To investigate carbon dynamics and establish ice wedge formation ages in Interior Alaska, we dated a late Pleistocene ice wedge, formerly assigned to Marine Isotope Stage (MIS) 3, and host sediments near Fairbanks, Alaska, with 24 radiocarbon analyses on wood, particulate organic carbon (POC), air-bubble CO₂, and dissolved organic carbon (DOC). Our new CO₂ and DOC ages are up to 11,170 yr younger than ice wedge POC ages, indicating that POC is detrital in origin. We conclude an ice wedge formation age between 28 and 22 cal ka BP during cold stadial conditions of MIS 2 and solar insolation minimum, possibly associated with Heinrich event 2 or the last glacial maximum. A DOC age for an ice lens in a thaw unconformity above the ice wedge returned a maximum age of 21,470 ± 200 cal yr BP. Our variable ¹⁴C data indicate recycling of older carbon in ancient permafrost terrain, resulting in radiocarbon ages significantly older than the period of ice-wedge activity. Release of ancient carbon with climatic warming will therefore affect the global ¹⁴C budget.     

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

Pinliang Dong and Qi Chen: LiDAR Remote Sensing and Applications

Mathematical Geosciences -