Products and Mechanism of the Gas Phase Reaction of Ozone with β-Pinene

Gas phase ozonolysis of -pinene was performedin a 570 l static reactor at 730 Torr and 296 K insynthetic air and the products were analysed by acombination of gas phase FTIR spectroscopy, HPLC andIC analyses of gas phase and aerosol samples,respectively. The reaction mechanism was investigatedby adding HCHO, HCOOH and H₂O as Criegeeintermediate scavenger and cyclohexane as OH radicalscavenger. Main identified products (yields inparentheses) in the presence of cyclohexane as OHradical scavenger were HCHO (0.65 ± 0.04),nopinone (0.16 ± 0.04), 3-hydroxy-nopinone (0.15± 0.05), CO₂ (0.20 ± 0.04), CO (0.030± 0.002), HCOOH (0.020 ± 0.002), the secondaryozonide of -pinene (0.16 ± 0.05), andcis-pinic acid (0.02 ± 0.01). The decompositionof the primary ozonide was found to yieldpredominantly the excited C₉-Criegee intermediateand HCHO (0.84 ± 0.04) and to a minor extent theexcited CH₂OO intermediate and nopinone (0.16± 0.04). Roughly 40% of the excitedC₉-Criegee intermediate becomes stabilised andcould be shown to react with HCHO, HCOOH and H₂O. The atmospherically important reaction of thestabilised C₉-Criegee intermediate with H₂Owas found to result in a nopinone increase of (0.35± 0.05) and in the formation of H₂O₂(0.24 ± 0.03). Based on the observed products,the unimolecular decomposition/isomerisationchannels of the C₉-Criegee intermediate arediscussed in terms of the hydroperoxide and esterchannels. Subsequent reactions of the nopinonylradical, formed in the hydroperoxide channel, lead tomajor products like 3-hydroxy-nopinone but also tominor products like cis-pinic acid. A mechanismfor the formation of this dicarboxylic acid isproposed and its possible role in aerosol formationprocesses discussed.     

Middle Campanian–lowermost Maastrichtian nannofossil and foraminiferal biostratigraphy of the northwestern Australian margin

The middle–late Campanian was marked by an increase in the bioprovinciality of calcareous microfossil assemblages into distinct Tethyan, Transitional, and Austral Provinces that persisted to the end of the Maastrichtian. The northwestern Australian margin belonged to the Transitional Province and the absence of key Tethyan marker species such as Radotruncana calcarata and Gansserina gansseri has led petroleum companies operating in the area to use the locally developed KCCM integrated calcareous microfossil zonation scheme. The KCCM zonation is a composite scheme comprising calcareous nannofossil (KCN), planktonic foraminiferal (KPF) and benthonic foraminiferal (KBF) zones. This paper presents the definitions and revisions of Zones KCCM8–19, from the highest occurrence (HO) of Aspidolithus parcus constrictus to the lowest occurrence (LO) of Ceratolithoides aculeus, and builds on our previous early–late Maastrichtian study. The presence of a middle–upper Campanian disconformity is confirmed by microfossil evidence from the Vulcan Sub-basin, Exmouth and Wombat plateaus, and the Southern Carnarvon Platform. In the Vulcan Sub-basin and on the Exmouth Plateau (ODP Hole 762C) the hiatus extends from slightly above the LO of common Rugoglobigerina rugosa to above the LO of Quadrum gothicum. On the Wombat Plateau (ODP Hole 761B) it spans from above the LO of Heterohelix semicostata to above the LO of Quadrum gothicum; and in the Southern Carnarvon Platform the disconformity has its longest duration from above the HO of Heterohelix semicostata to above the LO of Quadrum sissinghii. A significant revision of the events which define Zones KCCM18 and 19 was necessary owing to the observation that the LO of Ceratolithoides aculeus occurs below the HOs of Archaeoglobigerina cretacea and Stensioeina granulata incondita and the LO of common Rugoglobigerina rugosa. In the original zonation these events were considered to be coincident.     

中国中部南洛河流域地貌、黄土堆积与更新世古人类生存环境

本文结合最近获得的新资料,对南洛河流域的地貌、黄土沉积和更新世环境进行综合分析。结果表明,南洛河上、中游地貌表现为河流峡谷和山间盆地相间分布的特征,盆地中河流阶地发育; 下游为平缓的山前平原和低山丘陵。黄土在全流域的山顶、河流阶地和盆地等各种地貌部位均有分布。黄土沉积受地形影响较大,上游黄土堆积速率低、颗粒细; 在下游有风道直通的地方,黄土堆积速率高、颗粒粗。在不同地貌部位,黄土开始堆积的年代不同,黄土底界的年代从早更新世到晚更新世均有所见。对埋藏旧石器的年代研究表明,南洛河流域的古人类活动从早更新世晚期(约800ka)开始,到晚更新世后期(约30ka)结束,期间有多期遗存。初步的孢粉和有机碳同位素分析表明,这里曾是森林草原景观,冰期时,乔木植被以松属为主,C4类型草本减少; 而间冰期时,乔木植被以松属-榆科占主导地位,C4类植物增多。古人类在黄土堆积期和古土壤发育期都可能在这个地方活动,但这一认识需要更多的证据支持。丰富的石制品分布和较为连续的黄土沉积,使南洛河流域成为理解更新世人类行为与环境的重要区域。     

Acute toxicity of bromochlorinated seawater to selected estuarine species with a comparison to chlorinated seawater toxicity

The acute toxicity of bromochlorinated estuarine water (ca. 20%) was determined for several estuarine organisms. The most sensitive species were oysters (Crassostrea virginica, larvae and juveniles) and copepods (Acartia tonsa) with 48-h LC₅₀'s of 0·10 to 0·21 mg BrCl/litre. Palaemonetes pugio was most tolerant with a 96-h LC₅₀ of 0·70 mg BrCl/litre. The fish species tested (Menidia menidia, Brevoortia tyrannus and Leiostomus xanthurus) all had a 96-h LC₅₀ of 0·21–0·23 mg BrCl/litre.The BrCl toxicity data are compared with Cl₂ toxicity data for the same species. When the LC₅₀'s are expressed as equivalents per litre, BrCl is found to be two to four times less toxic than Cl₂. The ranking of species in terms of sensitivity is the same for both disinfectants.Some data are provided concerning the decay rates of BrCl and Cl₂ in estuarine water. BrCl was found to decay more rapidly than Cl₂ at higher ammonia levels (0·25 mg NH₄-N/litre). The question of chemical speciation is discussed with particular reference to the differential toxicities.     

Nature of the crust in Maine,USA: evidence from the Sebago batholith

 Neodymium and lead isotope and elemental data are presented for the Sebago batholith (293±2 Ma), the largest exposed granite in New England. The batholith is lithologically homogeneous, yet internally heterogeneous with respect to rare earth elements (REE) and Nd isotopic composition. Two-mica granites in the southern/central portion of the batholith (group 1) are characterized by REE patterns with uniform shapes [Ce_N/Yb_N (chondrite normalized) = 9.4–19 and Eu/Eu* (Eu anomaly) = 0.27–0.42] and ɛ _Nd(t) = −3.1 to −2.1. Peripheral two-mica granites (group 2), spatially associated with stromatic and schlieric migmatites, have a wider range of total REE contents and patterns with variable shapes (Ce_N/Yb_N = 6.1–67, Eu/Eu* = 0.20–0.46) and ɛ _Nd(t) = −5.6 to −2.8. The heterogeneous REE character of the group 2 granites records the effects of magmatic differentiation that involved monazite. Coarse-grained leucogranites and aplites have kinked REE patterns and low total REE, but have Nd isotope systematics similar to group 2 granites with ɛ _Nd(t) = −5.5 to −4.7. Rare biotite granites have steep REE patterns (Ce_N/Yb_N = 51–61, Eu/Eu* = 0.32–0.84) and ɛ _Nd(t) = −4.6 to −3.8. The two-mica granites have a restricted range in initial Pb isotopic composition (²⁰⁶Pb/²⁰⁴Pb = 18.41–18.75; ²⁰⁷Pb/²⁰⁴Pb = 15.60–15.68; ²⁰⁸Pb/²⁰⁴Pb = 38.21–38.55), requiring and old, high U/Pb (but not Th/U) source component. The Nd isotope data are consistent with magma derivation from two sources: Avalon-like crust (ɛ _Nd>−3), and Central Maine Belt metasedimentary rocks (ɛ _Nd<−4), without material input from the mantle. The variations in isotope systematics and REE patterns are inconsistent with models of disequilibrium melting which involved monazite. Received: 8 December 1995 / Accepted: 29 April 1996     

When hazard avoidance is not an option: lessons learned from monitoring the postdisaster Oso landslide,USA

On 22 March 2014, a massive, catastrophic landslide occurred near Oso, Washington, USA, sweeping more than 1 km across the adjacent valley flats and killing 43 people. For the following 5 weeks, hundreds of workers engaged in an exhaustive search, rescue, and recovery effort directly in the landslide runout path. These workers could not avoid the risks posed by additional large-scale slope collapses. In an effort to ensure worker safety, multiple agencies cooperated to swiftly deploy a monitoring and alerting system consisting of sensors, automated data processing and web-based display, along with defined communication protocols and clear calls to action for emergency management and search personnel. Guided by the principle that an accelerating landslide poses a greater threat than a steadily moving or stationary mass, the system was designed to detect ground motion and vibration using complementary monitoring techniques. Near real-time information was provided by continuous GPS, seismometers/geophones, and extensometers. This information was augmented by repeat-assessment techniques such as terrestrial and aerial laser scanning and time-lapse photography. Fortunately, no major additional landsliding occurred. However, we did detect small headscarp failures as well as slow movement of the remaining landslide mass with the monitoring system. This was an exceptional response situation and the lessons learned are applicable to other landslide disaster crises. They underscore the need for cogent landslide expertise and ready-to-deploy monitoring equipment, the value of using redundant monitoring techniques with distinct goals, the benefit of clearly defined communication protocols, and the importance of continued research into forecasting landslide behavior to allow timely warning.

     

Flood tide circulation near beaufort inlet, North Carolina: Implications for larval recruitment

Drifter tracks and shipboard CTD observations have revealed a number of distinct features of the flood tide circulation carrying water through Beaufort Inlet, North Carolina. One of the most noteworthy of these features is a nearshore jet in the flow carrying water to the inlet on a flood tide. Characterized by a shoreward increase in longshore flow, the jet produces a narrow coastal zone over which water is carried into the inlet. The jet appears to be principally a tidal phenomenon, as it is closely reproduced by a tidally-driven barotropic numerical model. The model results also indicate the jet may be a near-inlet feature. Model simulations of spring tide conditions show the jet confined to within 4 km of the inlet mouth. Another observed phenomenon, which is reproduced by the tidal model, is a distinct splitting of the flow entering the inlet, in which water passing through a particular inlet segment tends to move up-estuary along a well-defined path. An observed flow feature not reproduced by the tidal model is an eastward skew of the region over which water is drawn into the inlet on a flood tide. This asymmetry is unrelated to the local wind. Modeling results from a previous study suggest it may be due to convergent flow at the edge of the low salinity plume issuing from the inlet. Taken together, the results of this and other recent studies in the Beaufort Inlet region reveal the importance of nearshore currents on the eastern side of the inlet in delivering oceanic-spawned larvae to the estuarine system connected to the inlet.     

Comparing palaeolimnological and instrumental evidence of climate change for remote mountain lakes over the last 200 years

This paper compares the palaeolimnological evidence for climate change over the last 200 years with instrumental climate data for the same period at seven European remote mountain lakes. The sites are Øvre Neådalsvatn (Norway), Saanajärvi (Finland), Gossenköllesee (Austria), Hagelseewli (Switzerland), Jezero v Ledvici (Slovenia), Estany Redó (Spain, Pyrenees), and Niné Terianske Pleso (Slovakia). We used multiple regression analysis to transfer homogenised lowland air temperature records to each of the sites, and these reconstructions were validated using data from on-site automatic weather stations. These data showed that mean annual temperature has varied over the last 200 years at each site by between 1 and 2 °C, typical of the high frequency variability found throughout the Holocene, and appropriate, therefore, to test the sensitivity of the various proxy methods used. Sediment cores from each site were radiometrically dated using ²¹⁰Pb, ¹³⁷Cs and ²⁴¹Am and analysed for loss-on-ignition, C, N, S, pigments, diatoms, chrysophytes, Cladocera and chironomids. Comparisons between the proxy data and the instrumental data were based on linear regression analysis with the proxy data treated as response variables and the instrumental data (after smoothing using LOESS regressions) as predictor variables. The results showed few clear or consistent patterns with generally low or very low r² values. Highest values were found when the data were compared after smoothing using a broad span, indicating that some of the proxy data were capturing climate variability but only at a relatively coarse time resolution. Probable reasons for the weak performance of the methods used include inaccurate dating, especially for earlier time periods, the influence of confounding forcing factors at some sites e.g., air pollution, earthquakes, and the insensitivity of some methods to low amplitude climate forcing. Nevertheless, there were trends in some proxy records at a number of sites that had a relatively unambiguous correspondence with the instrumental climate records. These included organic matter and associated variables (C and N) and planktonic diatom assemblages at the majority of sites and chrysophytes and chironomids at a few sites. Overall for longer term studies of the Holocene, these results indicate the need to be cautious in the interpretation of proxy records, the importance of proxy method validation, the continuing need to use reinforcing multi-proxy approaches, and the need for careful site and method selection.