Novel 1H-Pyrrole-2,5-dione (maleimide) proxies for the assessment of photic zone euxinia

1H-Pyrrole-2,5-diones (maleimides) and 1-alkyl-2,3,6-trimethylbenzenes (aryl isoprenoids), degradation products of tetrapyrrole pigments and carotenoids respectively, were analysed and compared with pristane/phytane (Pr/Ph) ratios to reconstruct past redox conditions in three geologic sections. One section comes from the Middle–Late Devonian and was deposited before the Frasnian–Famennian boundary mass extinction. The two other sections span the Late Permian to the Early Triassic as well as the Late Triassic to the Early Jurassic, and recorded the Permian–Triassic (P/T) and Triassic–Jurassic (T/J) extinction events respectively. The 2-methyl-3-isobutyl-maleimide (Me,i-Bu maleimide) to 2-methyl-3-ethyl-maleimide (Me,Et maleimide) and 2-methyl-3-npropyl- maleimide (Me,n-Pr maleimide) to Me,Et maleimide ratios (Me,i-Bu/Me,Et and Me,n-Pr/Me,Et ratios) in the studied sections revealed amoderate to strong negative correlation to the aryl isoprenoid ratio (AIR), defined as (C13–C17 1-alkyl-2,3,6-trimethylbenzenes)/(C18–C22 1-alkyl-2,3,6-trimethylbenzenes), indicating that these maleimide ratios can be used as robust, specific indicators of photic zone euxinia (PZE). These results agreed with Pr/Ph ratios, which were used as diagnostic indicators to differentiate between oxic and anoxic conditions. In agreement with previous studies, the novel maleimide proxies suggest that all three mass extinctions werelargely characterised by PZE depositional conditions

Re-Os geochronology and isotope systematics, and organic and sulfur geochemistry of the middle-late Paleocene Waipawa Formation, New Zealand: Insights into early Paleogene seawater Os isotope composition

In the middle–late Paleocene, a marine, organic-rich sedimentary unit (Waipawa Formation [Fm]) in which the organic matter was derived mainly from terrestrial plants was deposited in many of New Zealand's sedimentary basins. The unique organofacies of this formation has not been identified in any other time interval within the geological history of the Southwest Pacific, indicating that unusual climatic and oceanographic conditions likely prevailed during this time. It has, therefore, attracted wide scientific interest due to its significance for regional and global reconstruction of the early Paleogene transitional climate as well as potential for oil and gas production. Scarcity of age-diagnostic fossils, presence of unconformities and lack of volcanic interbeds have, however, hindered precise dating and correlations of all the known occurrences of the formation. Here, rhenium‑osmium (Re-Os) geochronology has yielded the first radiometric age for the formation (57.5 ± 3.5 Ma), which is consistent with available biostratigraphic age determinations (59.4–58.7 Ma). Further, a comparison of Re-Os, bulk pyrolysis, sulfur and palynofacies data for the Waipawa Fm with those of more typical marine sediments such as the underlying Whangai Fm supports the interpretation that the chelating precursors or fundamental binding sites responsible for uptake of Re and Os are present in all types of organic matter, and that these elements have a greater affinity for organic chelating sites than for sulfides. The results also indicate that sedimentation rate may not play a dominant role in enhanced uptake of Re and Os by organic-rich sedimentary rocks. The initial 187Os/188Os values for the Waipawa (~0.28) and Whangai (~0.36) formations are broadly similar to those reported for coeval pelagic sediments from the central Pacific Ocean, further constraining the low-resolution marine 187Os/188Os record of the Paleocene. We present a compilation of 187Os/188Os values from organic-rich sedimentary rocks spanning the period between 70 and 50 Ma which shows that seawater Os gradually became less radiogenic from the latest Cretaceous, reaching a minimum value in the earliest late Paleocene (~59 Ma) during the deposition of Waipawa Fm, and then increased through the later Paleocene and into the early Eocene. The composite Os isotope record broadly correlates with global temperature (δ18O and TEX86) and carbon isotope (δ13C) records from the middle Paleocene to early Eocene, which is inferred to reflect climate-modulated changes in continental weathering patterns

Distributions and compound-specific isotopic signatures of sedimentary chlorins reflect the composition of photoautotrophic communities and their carbon and nitrogen sources in Swiss lakes and the Black Sea

We examined the distributions of tetrapyrrole pigments (i.e. intact chlorophylls and bacteriochlorophylls, pheopigments) as well as their compound-specific carbon and nitrogen isotopic compositions in the sediments of three Swiss lakes (Lakes Rotsee, Cadagno and Zurich) and the Black Sea to investigate the biogeochemical cycling of carbon and nitrogen mediated by phototrophic eukaryotes (algae) and bacteria. The factors controlling chlorin isotope variations are discussed and the feasibility to use chlorins as indicators for reconstructions of surface water environments is evaluated. Chlorophyll a and its derivatives including pheophytin a, a pheophytin a epimer, pyropheophytin a, 132,173-cyclopheophorbide-a-enol, chlorophyllone a as well as steryl and carotenol chlorin esters were detected in all sediments. The presence of bacteriochlorophylls e and their derivatives confirmed the presence of brown strains of green phototrophic sulfur bacteria (Chlorobiaceae; GSB) in all three lakes. In the shallower Lakes Rotsee and Cadagno, purple sulfur bacteria (Chromatiaceae; PSB) were also present as confirmed by bacteriochlorophyll a derivatives. Despite the different degrees of water column hypoxia at the studied sites, the chlorins in all sediments were attributed to rapid transformation of intact tetrapyrroles and the formation of related pheopigments.The scatter of compound-specific carbon isotopic compositions of Chl a and its derivatives resulted from different timing of pheopigment formation, likely due to the interaction of blooms of various phytoplankton communities at different times of the year and the variable degrees of carbon limitation and/or different contributions of recycled organic matter (OM). The nitrogen isotopic composition of the chloropigments mainly derived from nitrate assimilation in Lake Zurich and the Black Sea, whereas ammonium and nitrate assimilation were predominant in Lake Rotsee. In the epilimnion of the meromictic Lake Cadagno, dissolved organic nitrogen (DON) supplied to the surface water from ammonium assimilation in the chemocline may be the main nitrogen source. Phototrophic sulfur bacteria in Lakes Rotsee and Cadagno thrived mainly under dissolved organic carbon depleted conditions within the chemocline and in the hypolimnion. GSB may use predominantly ammonium and at least in Lake Cadagno also perform N2 fixation. In contrast, the nitrogen source of PSB could not be reconstructed with d15N values of bacteriochlorins, because nitrogen isotopic fractionation during BChl a synthesis seems to be almost independent of the assimilated substrate

Comparison of next-generation portable pollution monitors to measure exposure to PM2.5 from household air pollution in Puno, Peru.

Assessment of personal exposure to PM2.5 is critical for understanding intervention effectiveness and exposure-response relationships in household air pollution studies. In this pilot study, we compared PM2.5 concentrations obtained from two next-generation personal exposure monitors (the Enhanced Children MicroPEM or ECM; and the Ultrasonic Personal Air Sampler or UPAS) to those obtained with a traditional Triplex Cyclone and SKC Air Pump (a gravimetric cyclone/pump sampler). We co-located cyclone/pumps with an ECM and UPAS to obtain 24-hour kitchen concentrations and personal exposure measurements. We measured Spearmen correlations and evaluated agreement using the Bland-Altman method. We obtained 215 filters from 72 ECM and 71 UPAS co-locations. Overall, the ECM and the UPAS had similar correlation (ECM ρ = 0.91 vs UPAS ρ = 0.88) and agreement (ECM mean difference of 121.7 µg/m3 vs UPAS mean difference of 93.9 µg/m3 ) with overlapping confidence intervals when compared against the cyclone/pump. When adjusted for the limit of detection, agreement between the devices and the cyclone/pump was also similar for all samples (ECM mean difference of 68.8 µg/m3 vs UPAS mean difference of 65.4 µg/m3 ) and personal exposure samples (ECM mean difference of -3.8 µg/m3 vs UPAS mean difference of -12.9 µg/m3 ). Both the ECM and UPAS produced comparable measurements when compared against a cyclone/pump setup

Compound-specific carbon and nitrogen isotopic compositions of chlorophyll a and its derivatives reveal the eutrophication history of Lake Zurich (Switzerland)

© 2016 Elsevier B.V. To reconstruct the impact of eutrophication on phototrophic communities and the biogeochemical cycling of carbon and nitrogen in the surface water, we investigated the distributions and carbon and nitrogen isotopic compositions (d13C and d15N values) of chlorins in the sediments of Lake Zurich. The chlorin distributions were dominated by chlorophyll a (Chl a) and its derivatives, which reflect rapid degradation to the pheopigments in the water column and sediments of the lake. The d13C values of these sedimentary chlorins followed the historical trends of eutrophication and reoligotrophication, except in the surface sediments, which were characterised by higher relative contributions of aged, redeposited organic matter (OM). The d13C values of the sedimentary chlorins together with bulk sediment d13C values and C/N ratios indicate that the phototrophic communities in the lake used a 13C-depleted carbon source, which is mainly of aquatic origin. The d15N values of chlorins reflect the predominance of nitrate assimilating phototrophs, especially the non-N2-fixing cyanobacterium Planktothrix rubescens prevalent during sediment deposition. Shifts in d15N values of Chl a followed mostly the trends in eutrophication and reoligotrophication, but were also affected by community assemblage shifts to diatoms and/or other cyanobacteria at the end of the 19th century and during the eutrophication maximum in the 1970s.The lower d15NChl-a values in the surface sediments coincide with increasing nitrogen to phosphorus ratios and reduced water column mixing that characterise the recent reoligotrophication period and may explain the predominance of P. rubescens in Lake Zurich. In contrast, the higher contributions of laterally transported OM explains the large offset of d15N values of the pheopigments relative to Chl a, which is supported by the high radiocarbon age of the surface sediments

Regional integration clusters and optimum customs Unions: a machine-learning approach

This paper proposes a new method to evaluate the composition of regional arrangements focused on increasing intraregional trade and economic integration. In contrast to previous studies which take the country composition of these arrangements as given, our method uses a network clustering algorithm adapted from the machine learning literature to identify, in a data-driven way, those groups of neighboring countries that are most integrated with each other. Using the obtained landscape of regional integration clusters (RICs) as benchmark, we then apply our method to critically assess the composition of real-world customs unions. Our results indicate that there is considerable variation across customs unions as to their distance to the RICs emerging from the clustering algorithm, suggesting that some customs unions are relatively more driven by ‘natural’ economic forces, as opposed to political considerations. Our results also point to several testable hypotheses related to the geopolitical configuration of customs unions

Potential of biogas production to reduce firewood consumption in remote high-elevation Himalayan communities in Nepal

Remote communities in the Nepalese mountains above 2500 m a.s.l. belong to the most precarious in the world. Inhabitants struggle for the minimum in terms of safe drinking water, food and sanitation. Reliable, affordable and clean energy for cooking, room heating and warm water for personal hygiene is often lacking and dependency on firewood very high. The remoteness and unlikeliness of electric grid connection in the coming decades make a diversified energy supply from renewable local resources crucial. Small-scale anaerobic digestion (AD) of organic substrates has been used for long in rural areas of developing countries to produce biogas as energy source and recover residue as organic fertilizer. AD is challenging at high elevations due to year around lower ambient temperatures and lower annual biomass production per area compared to lowlands. Nevertheless, examples of operational household AD exist even above 3000 m a.s.l. in the Andes. Here we compare firewood consumption with biogas potential from organic substrates in a community with 39 households at 3150 m a.s.l. in Jumla District, Nepal. In five households with varying numbers of members and animals kept, mean firewood use and its energy content per capita (cap) and day (d) were 2.1 kg or ca. 25 MJ in spring and 2.3 kg or ca. 28 MJ in winter. Easily available substrates include cow, sheep and horse dung from overnight shelters and human excrements from pit latrines, amounting on average to 1.7 kg wet weight (kgww) cap−1 d−1 in spring and 2.2 kgww cap−1 d−1 in winter. Adjusted to normal conditions (Nm3 at 0 °C, 1013.15 hPa), these substrates yielded on average 0.08 Nm3 cap−1 d−1 biogas in spring and 0.12 Nm3 cap−1 d−1 in winter (35–60% methane content) in biochemical methane potential (BMPs) tests at 36 °C. This could provide up to 60% of basic cooking needs on average and up to 75% in a “typical” household in terms of members and animals kept. Of the overall thermal energy needs including also room heating ca. 10–20% could be covered, substituting 0.1–0.4 (mean: 0.2) kg firewood cap−1 d−1. If only animal dung and human excrements are considered, no competition for resources arises as residues can still be used as organic fertilizer. This study supports the design and introduction of planned pilot digesters integrated into on-going community development including pit latrines for substrate availability, greenhouses as possible way of thermal insulation, and planned pico-hydropower plants to use excess electricity during the night for digester heating

Chimney Stove Intervention to Reduce Long-term Wood Smoke Exposure Lowers Blood Pressure among Guatemalan Women

Background and Objective: RESPIRE, a randomized trial of an improved cookstove, was conducted in Guatemala to assess health effects of long-term reductions in wood smoke exposure. Given the evidence that ambient particles increase blood pressure, we hypothesized that the intervention would lower blood pressure. Methods: Two study designs were used: a) between-group comparisons based on randomized stove assignment, and b) before-and-after comparisons within subjects before and after they received improved stoves. From 2003 to 2005, we measured personal fine particle (particulate matter with aerodynamic diameter 38 years of age from the chimney woodstove intervention group (49 subjects) and traditional open wood fire control group (71 subjects). Measures were repeated up to three occasions. Results: Daily average PM2.5 exposures were 264 and 102 μg/m3 in the control and intervention groups, respectively. After adjusting for age, body mass index, an asset index, smoking, secondhand tobacco smoke, apparent temperature, season, day of week, time of day, and a random subject intercept, the improved stove intervention was associated with 3.7 mm Hg lower SBP [95% confidence interval (CI), −8.1 to 0.6] and 3.0 mm Hg lower DBP (95% CI, −5.7 to −0.4) compared with controls. In the second study design, among 55 control subjects measured both before and after receiving chimney stoves, similar associations were observed. Conclusion: The between-group comparisons provide evidence, particularly for DBP, that the chimney stove reduces blood pressure, and the before-and-after comparisons are consistent with this evidence