Implementing constructed wetlands for nutrient reduction at watershed scale: Opportunity to link models and real-world execution.

The negative effects of nutrient pollution in streams, rivers, and downstream waterbodies remain widespread global problems. Understanding the cost-effectiveness of different strategies for mitigating nutrient pollution is critical to making informed decisions and defining expectations that best utilize limited resources, which is a research priority for the US Environmental Protection Agency. To this end, we modeled nutrient management practices including residue management, cover crops, filter strips, grassed waterways, constructed wetlands, and reducing fertilizer in the upper East Fork of the Little Miami River, an 892 km2 watershed in southwestern Ohio, United States. The watershed is 64% agriculture with 422 km2 of row crops contributing an estimated 71% of the system's nutrient load. The six practices were modeled to treat row crop area, and among them, constructed wetlands ranked highest for their low costs per kilogram of nutrient removed. To meet a 42% phosphorus (P) reduction target for row crops, the model results suggested that the runoff from 85.5% of the row crop area would need to be treated by the equivalent of 3.61 km2 of constructed wetlands at an estimated cost of US$2.4 million annually (or US$48.5 million over a 20-year life cycle). This prompted a series of projects designed to understand the feasibility (defined in terms of build, treatment, and cost potential) of retrofitting the system with the necessary extent of constructed wetlands. The practicalities of building this wetland coverage into the system, while leading to innovation in unit-level design, has highlighted the difficulty of achieving the nutrient reduction target with wetlands alone. Approximately US$1.2 million have been spent on constructing 0.032 km2 of wetlands thus far and a feasibility analysis suggests a cost of US$38 million for an additional 0.409 km2. However, the combined expenditures would only achieve an estimated 13% of the required treatment. The results highlight the potential effectiveness of innovative design strategies for nutrient reduction and the importance of considering realistic field-scale build opportunities, which include accounting for acceptance among landowners, in watershed-scale nutrient reduction simulations using constructed wetlands.

Rapid and precise measurement of carbonate clumped isotopes using laser spectroscopy.

Carbonate clumped isotope abundance is an important paleothermometer, but measurement is difficult, slow, and subject to cardinal mass (m/z) interferences using isotope ratio mass spectrometry (IRMS). Here, we describe an optical spectroscopic measurement of carbonate clumped isotopes. We have adapted a tunable infrared laser differential absorption spectrometer (TILDAS) system to measure the abundances of four CO2 isotopologues used for clumped isotope thermometry. TILDAS achieves the same precision (0.01‰ SE) as IRMS measurements rapidly (∼50 min per carbonate analysis) and using small samples (<2 mg of calcite), without making assumptions about 17O abundance in the sample. A temperature calibration based on 406 analyses of CO2 produced by digestion of 51 synthetic carbonates equilibrated at 6° to 1100°C is consistent with results for natural carbonates and previous calibrations. Our system results were indistinguishable from IRMS systems after replicating the InterCarb interlaboratory calibration. Measurement by TILDAS could change the landscape for clumped isotope analysis.

The perceived costs and benefits of mentoring college students with intellectual disability on stereotype consistent and inconsistent tasks.

BACKGROUND: According to the stereotype content model, individuals with intellectual disability are perceived as having greater warmth-related traits (e.g. sociable and humorous) and fewer competence-related traits (e.g. independence and intelligence). METHODS: We examined college students' perceived costs and benefits of mentoring peers with intellectual disability on stereotype-consistent (i.e. socially oriented) or inconsistent (i.e. academically oriented) tasks. Participants read about peer mentoring programmes that helped college students with or without intellectual disability on socially or academically oriented tasks before reporting their perceived costs and benefits of peer mentoring. RESULTS: Mentoring students with intellectual disability was associated with greater benefits (i.e. connectedness between mentors and students, student utility and mentor benefits) on academically oriented tasks but greater costs for mentors on socially oriented tasks. Additionally, participants reported that they would experience greater positive feelings if they were to mentor a student with an intellectual disability. However, the perceived benefits to the student and some costs (i.e. discomfort, paternalism and costs to student) were not influenced by whether the student had an intellectual disability and the type of mentoring task. DISCUSSION: Results indicate individuals find greater rewards working with individuals with intellectual disability on stereotype-inconsistent tasks and offer suggestions for postsecondary education peer mentoring programmes.

Interleukin-6, C-reactive protein, fibrinogen, and risk of recurrence after ischaemic stroke: Systematic review and meta-analysis.

BACKGROUND: Recent randomised trials showed benefit for anti-inflammatory therapies in coronary disease but excluded stroke. The prognostic value of blood inflammatory markers after stroke is uncertain and guidelines do not recommend their routine measurement for risk stratification. METHODS: We performed a systematic review and meta-analysis of studies investigating the association of C-reactive protein (CRP), interleukin-6 (IL-6) and fibrinogen and risk of recurrent stroke or major vascular events (MVEs). We searched EMBASE and Ovid Medline until 10/1/19. Random-effects meta-analysis was performed for studies reporting comparable effect measures. RESULTS: Of 2,515 reports identified, 39 met eligibility criteria (IL-6, n = 10; CRP, n = 33; fibrinogen, n = 16). An association with recurrent stroke was reported in 12/26 studies (CRP), 2/11 (fibrinogen) and 3/6 (IL-6). On random-effects meta-analysis of comparable studies, CRP was associated with an increased risk of recurrent stroke [pooled hazard ratio (HR) per 1 standard-deviation (SD) increase in loge-CRP (1.14, 95% CI 1.06-1.22, p < 0.01)] and MVEs (pooled HR 1.21, CI 1.10-1.34, p < 0.01). Fibrinogen was also associated with recurrent stroke (HR 1.26, CI 1.07-1.47, p < 0.01) and MVEs (HR 1.31, 95% CI 1.15-1.49, p < 0.01). Trends were identified for IL-6 for recurrent stroke (HR per 1-SD increase 1.17, CI 0.97-1.41, p = 0.10) and MVEs (HR 1.22, CI 0.96-1.55, p = 0.10). CONCLUSION: Despite evidence suggesting an association between inflammatory markers and post-stroke vascular recurrence, substantial methodological heterogeneity was apparent between studies. Individual-patient pooled analysis and standardisation of methods are needed to determine the prognostic role of blood inflammatory markers and to improve patient selection for randomised trials of inflammatory therapies.

Rapid and Precise Analysis of Carbon Dioxide Clumped Isotopic Composition by Tunable Infrared Laser Differential Spectroscopy.

The high precision measurement of doubly substituted ("clumped") isotopologues in CO2 is a topic of significant interest in isotope geochemistry. Here we describe the performance of a new isotope ratio laser spectrometer using tunable infrared laser differential absorption spectroscopy (TILDAS). The TILDAS instrument has two continuous-wave lasers to simultaneously measure the four isotopologues involved in the 12C16O2 + 13C16O18O ⇆ 13C16O2 + 12C16O18O exchange reaction. CO2 samples are trapped in a low volume (∼250 mL) optical multipass cell with a path length of 36 m. Each sample is compared to a reference gas, and clumped isotopologue precision of 0.01‰ (SE) is achieved within 20 min for 15 µmol samples. Similar precision is also achieved for bulk isotopic composition. The degree of rare isotope clumping in excess of strictly random distribution (Δ16O13C18O) measured by this TILDAS instrument varies linearly with theoretically calculated values and shows a very weak dependence on bulk isotopic composition.

Precise Measurements of 12CH2D2 by Tunable Infrared Laser Direct Absorption Spectroscopy.

We present precise measurements of doubly deuterated methane (12CH2D2) in natural methane samples using tunable infrared laser direct absorption spectroscopy (TILDAS). Using a 413 m optical path length astigmatic Herriott cell and two quantum cascade lasers (QCLs) scanning the spectral regions of 1090.46 ± 0.1 and 1200.23 ± 0.1 cm-1, the instrument simultaneously measures the five main isotopologues of methane. The ratios 13CH3D/12CH4 and 12CH2D2/12CH4 are measured at 0.01‰ and 0.5‰ (1σ) instrumental precision, respectively. The instrumental accuracy was assessed by measuring a series of methane gases with a range of δ13C and δD values but with the abundances of all isotopologues driven to thermal equilibrium at 250 °C. The estimated accuracy of Δ12CH2D2 is 1‰ (1σ) on the basis of the results of the heated methane samples. This new TILDAS instrument provides a simple and rapid technique to explore the sources of methane in the environment.

More efficient North Atlantic carbon pump during the Last Glacial Maximum.

During the Last Glacial Maximum (LGM; ~20,000 years ago), the global ocean sequestered a large amount of carbon lost from the atmosphere and terrestrial biosphere. Suppressed CO2 outgassing from the Southern Ocean is the prevailing explanation for this carbon sequestration. By contrast, the North Atlantic Ocean-a major conduit for atmospheric CO2 transport to the ocean interior via the overturning circulation-has received much less attention. Here we demonstrate that North Atlantic carbon pump efficiency during the LGM was almost doubled relative to the Holocene. This is based on a novel proxy approach to estimate air-sea CO2 exchange signals using combined carbonate ion and nutrient reconstructions for multiple sediment cores from the North Atlantic. Our data indicate that in tandem with Southern Ocean processes, enhanced North Atlantic CO2 absorption contributed to lowering ice-age atmospheric CO2.

Enhanced climate instability in the North Atlantic and southern Europe during the Last Interglacial.

Considerable ambiguity remains over the extent and nature of millennial/centennial-scale climate instability during the Last Interglacial (LIG). Here we analyse marine and terrestrial proxies from a deep-sea sediment sequence on the Portuguese Margin and combine results with an intensively dated Italian speleothem record and climate-model experiments. The strongest expression of climate variability occurred during the transitions into and out of the LIG. Our records also document a series of multi-centennial intra-interglacial arid events in southern Europe, coherent with cold water-mass expansions in the North Atlantic. The spatial and temporal fingerprints of these changes indicate a reorganization of ocean surface circulation, consistent with low-intensity disruptions of the Atlantic meridional overturning circulation (AMOC). The amplitude of this LIG variability is greater than that observed in Holocene records. Episodic Greenland ice melt and runoff as a result of excess warmth may have contributed to AMOC weakening and increased climate instability throughout the LIG.

Repeated storage of respired carbon in the equatorial Pacific Ocean over the last three glacial cycles.

As the largest reservoir of carbon exchanging with the atmosphere on glacial-interglacial timescales, the deep ocean has been implicated as the likely location of carbon sequestration during Pleistocene glaciations. Despite strong theoretical underpinning for this expectation, radiocarbon data on watermass ventilation ages conflict, and proxy interpretations disagree about the depth, origin and even existence of the respired carbon pool. Because any change in the storage of respiratory carbon is accompanied by corresponding changes in dissolved oxygen concentrations, proxy data reflecting oxygenation are valuable in addressing these apparent inconsistencies. Here, we present a record of redox-sensitive uranium from the central equatorial Pacific Ocean to identify intervals associated with respiratory carbon storage over the past 350 kyr, providing evidence for repeated carbon storage over the last three glacial cycles. We also synthesise our data with previous work and propose an internally consistent picture of glacial carbon storage and equatorial Pacific Ocean watermass structure.

High-Precision Simultaneous 18O/16O, 13C/12C, and 17O/16O Analyses for Microgram Quantities of CaCO3 by Tunable Infrared Laser Absorption Spectroscopy.

Stable isotope ratios (18O/16O, 13C/12C, and 17O/16O) in carbonates have contributed greatly to the understanding of Earth and planetary systems, climates, and history. The current method for measuring isotopologues of CO2 derived from CaCO3 is primarily gas-source isotope ratio mass spectroscopy (IRMS). However, IRMS has drawbacks, such as mass overlap by multiple CO2 isotopologues and contaminants, the requirement of careful sample purification, and the use of major instrumentation needing permanent installation and a high power electrical supply. Here, we report simultaneous 18O/16O, 13C/12C, and 17O/16O analyses for microgram quantities of CaCO3 using a tunable mid-infrared laser absorption spectroscopy (TILDAS) system, which has no mass overlap problem and yields high sensitivity/precision measurements on small samples, as small as 0.02 µmol of CO2 (equivalent to 2 µg of CaCO3) with standard errors of less than 0.08 ‰ for 18O/16O and 13C/12C (±0.136 ‰ and ±0.387 ‰ repeatability; n = 10). In larger samples of CO2, 0.68 µmol (or 68 µg of CaCO3), standard error is less than 0.04 ‰ for 18O/16O and 13C/12C (< ±0.1 ‰ repeatability; n = 10) and 0.03 ‰ for 17O/16O (±0.069 ‰ repeatability; n = 10). We also show, for the first time, the relationship between 17O/16O ratios measured using the TILDAS system and published δ17O values of international standard materials (NBS-18 and -19) measured by IRMS. The benchtop TILDAS system, with cryogen-free sample preparation vacuum lines for microgram quantities of carbonates, is therefore a significant advance in carbonate stable isotope ratio geochemistry and is a new alternative to conventional IRMS.

Outcomes of endovascular treatment for acute large-vessel ischaemic stroke more than 6 h after symptom onset.

BACKGROUND AND OBJECTIVES: Benefit from endovascular thrombectomy (EVT) for large-vessel occlusion (LVO) acute ischaemic stroke (AIS) is well demonstrated. Furthermore, emerging evidence supports efficacy in appropriately selected patients treated beyond current recommendations of 6 h. We evaluated clinical outcomes in patients undergoing late EVT at our institution. METHODS: Retrospective review of prospectively collected clinical database on 355 patients who underwent EVT for LVO AIS. Data collected consisted of patient demographics, radiological findings and outcome details. Outcomes, including 90-day functional status, recanalization, symptomatic intracranial haemorrhage (sICH) and 90-day mortality, for patients undergoing EVT <6 h, >6 h, and >7.3 h, were compared. RESULTS: A total of 355 patients underwent EVT for LVO AIS at our institution during the review period, with 74 (21%) patients treated ≥6 h from symptom onset. Successful recanalization was achieved in 285 (80%) patients, with 228 (81%) achieving a mTICI ≥2b in the <6 h group, and 57 (77%) in the >6 h group (P = 0.429). Ninety-day functional independence (mRS 0-2) was achieved in 162 (46%) patients, with 130 (46%) achieving a mRS of 0-2 in the <6 h group, and 32 (43%) in the >6 h group (P = 0.643). No significant differences were found in rates of sICH or 90-day mortality. No significant differences in functional independence, recanalization rates, sICH or mortality were identified in patients treated with EVT >7.3 h compared to <7.3 h. CONCLUSIONS: In appropriately selected patients, EVT >6 h was associated with comparable outcomes to those treated <6 h. These data support a physiological approach to patient selection.

Seasonality of temperate forest photosynthesis and daytime respiration.

Terrestrial ecosystems currently offset one-quarter of anthropogenic carbon dioxide (CO2) emissions because of a slight imbalance between global terrestrial photosynthesis and respiration. Understanding what controls these two biological fluxes is therefore crucial to predicting climate change. Yet there is no way of directly measuring the photosynthesis or daytime respiration of a whole ecosystem of interacting organisms; instead, these fluxes are generally inferred from measurements of net ecosystem-atmosphere CO2 exchange (NEE), in a way that is based on assumed ecosystem-scale responses to the environment. The consequent view of temperate deciduous forests (an important CO2 sink) is that, first, ecosystem respiration is greater during the day than at night; and second, ecosystem photosynthetic light-use efficiency peaks after leaf expansion in spring and then declines, presumably because of leaf ageing or water stress. This view has underlain the development of terrestrial biosphere models used in climate prediction and of remote sensing indices of global biosphere productivity. Here, we use new isotopic instrumentation to determine ecosystem photosynthesis and daytime respiration in a temperate deciduous forest over a three-year period. We find that ecosystem respiration is lower during the day than at night-the first robust evidence of the inhibition of leaf respiration by light at the ecosystem scale. Because they do not capture this effect, standard approaches overestimate ecosystem photosynthesis and daytime respiration in the first half of the growing season at our site, and inaccurately portray ecosystem photosynthetic light-use efficiency. These findings revise our understanding of forest-atmosphere carbon exchange, and provide a basis for investigating how leaf-level physiological dynamics manifest at the canopy scale in other ecosystems.

North Atlantic ocean circulation and abrupt climate change during the last glaciation.

The most recent ice age was characterized by rapid and hemispherically asynchronous climate oscillations, whose origin remains unresolved. Variations in oceanic meridional heat transport may contribute to these repeated climate changes, which were most pronounced during marine isotope stage 3, the glacial interval 25 thousand to 60 thousand years ago. We examined climate and ocean circulation proxies throughout this interval at high resolution in a deep North Atlantic sediment core, combining the kinematic tracer protactinium/thorium (Pa/Th) with the deep water-mass tracer, epibenthic δ(13)C. These indicators suggest reduced Atlantic overturning circulation during every cool northern stadial, with the greatest reductions during episodic Hudson Strait iceberg discharges, while sharp northern warming followed reinvigorated overturning. These results provide direct evidence for the ocean's persistent, central role in abrupt glacial climate change.

Large deglacial shifts of the Pacific Intertropical Convergence Zone.

The position of the Intertropical Convergence Zone (ITCZ) is sensitive to changes in the balance of heat between the hemispheres which has fundamental implications for tropical hydrology and atmospheric circulation. Although the ITCZ is thought to experience the largest shifts in position during deglacial stadial events, the magnitude of shifts has proven difficult to reconstruct, in part because of a paucity of high-resolution records, particularly those including spatial components. Here we track the position of the ITCZ from 150 to 110 ka at three sites in the central equatorial Pacific at sub-millennial time resolution. Our results provide evidence of large, abrupt changes in tropical climate during the penultimate deglaciation, coincident with North Atlantic Heinrich Stadial 11 (∼136-129 ka). We identify this event both as a Northern Hemisphere increase in aeolian dust and as a shift in the mean position of the ITCZ a minimum of 4° southwards at 160° W.

No iron fertilization in the equatorial Pacific Ocean during the last ice age.

The equatorial Pacific Ocean is one of the major high-nutrient, low-chlorophyll regions in the global ocean. In such regions, the consumption of the available macro-nutrients such as nitrate and phosphate is thought to be limited in part by the low abundance of the critical micro-nutrient iron. Greater atmospheric dust deposition could have fertilized the equatorial Pacific with iron during the last ice age--the Last Glacial Period (LGP)--but the effect of increased ice-age dust fluxes on primary productivity in the equatorial Pacific remains uncertain. Here we present meridional transects of dust (derived from the (232)Th proxy), phytoplankton productivity (using opal, (231)Pa/(230)Th and excess Ba), and the degree of nitrate consumption (using foraminifera-bound δ(15)N) from six cores in the central equatorial Pacific for the Holocene (0-10,000 years ago) and the LGP (17,000-27,000 years ago). We find that, although dust deposition in the central equatorial Pacific was two to three times greater in the LGP than in the Holocene, productivity was the same or lower, and the degree of nitrate consumption was the same. These biogeochemical findings suggest that the relatively greater ice-age dust fluxes were not large enough to provide substantial iron fertilization to the central equatorial Pacific. This may have been because the absolute rate of dust deposition in the LGP (although greater than the Holocene rate) was very low. The lower productivity coupled with unchanged nitrate consumption suggests that the subsurface major nutrient concentrations were lower in the central equatorial Pacific during the LGP. As these nutrients are today dominantly sourced from the Subantarctic Zone of the Southern Ocean, we propose that the central equatorial Pacific data are consistent with more nutrient consumption in the Subantarctic Zone, possibly owing to iron fertilization as a result of higher absolute dust fluxes in this region. Thus, ice-age iron fertilization in the Subantarctic Zone would have ultimately worked to lower, not raise, equatorial Pacific productivity.

How fluorescent labelling alters the solution behaviour of proteins.

A complete understanding of the role of molecular anisotropy in directing the self assembly of colloids and proteins remains a challenge for soft matter science and biophysics. For proteins in particular, the complexity of the surface at a molecular level poses a challenge for any theoretical and numerical description. A soft matter approach, based on patchy models, has been useful in describing protein phase behaviour. In this work we examine how chemical modification of the protein surface, by addition of a fluorophore, affects the physical properties of protein solutions. By using a carefully controlled experimental protein model (human gamma-D crystallin) and numerical simulations, we demonstrate that protein solution behaviour defined by anisotropic surface effects can be captured by a custom patchy particle model. In particular, the chemical modification is found to be equivalent to the addition of a large hydrophobic surface patch with a large attractive potential energy well, which produces a significant increase in the temperature at which liquid-liquid phase separation occurs, even for very low fractions of fluorescently labelled proteins. These results are therefore directly relevant to all applications based on the use of fluorescent labelling by chemical modification, which have become increasingly important in the understanding of biological processes and biophysical interactions.

Crustal fluid and ash alteration impacts on the biosphere of Shikoku Basin sediments, Nankai Trough, Japan.

We present data from sediment cores collected from IODP Site C0012 in the Shikoku Basin. Our site lies at the Nankai Trough, just prior to subduction of the 19 Ma Philippine Sea plate. Our data indicate that the sedimentary package is undergoing multiple routes of electron transport and that these differing pathways for oxidant supply generate a complex array of metabolic routes and microbial communities involved in carbon cycling. Numerical simulations matched to pore water data document that Ca(2+) and Cl(1-) are largely supplied via diffusion from a high-salinity (44.5 psu) basement fluid, which supports the presence of halophile Archean communities within the deep sedimentary package that are not observed in shallow sediments. Sulfate supply from basement supports anaerobic oxidation of methane (AOM) at a rate of ~0.2 pmol cm(-3) day(-1) at ~400 mbsf. We also note the disappearance of δ-Proteobacteria at 434 mbsf, coincident with the maximum in methane concentration, and their reappearance at 463 mbsf, coinciding with the observed deeper increase in sulfate concentration toward the basement. We did not, however, find ANME representatives in any of the samples analyzed (from 340 to 463 mbsf). The lack of ANME may be due to an overshadowing effect from the more dominant archaeal phylotypes or may indicate involvement of unknown groups of archaea in AOM (i.e., unclassified Euryarchaeota). In addition to the supply of sulfate from a basement aquifer, the deep biosphere at this site is also influenced by an elevated supply of reactive iron (up to 143 µmol g(-1)) and manganese (up to 20 µmol g(-1)). The effect of these metal oxides on the sulfur cycle is inferred from an accompanying sulfur isotope fractionation much smaller than expected from traditional sulfate-reducing pathways. The detection of the manganese- and iron-reducer γ-Proteobacteria Alteromonas at 367 mbsf is consistent with these geochemical inferences.

Design and performance of a dual-laser instrument for multiple isotopologues of carbon dioxide and water.

A design and results for an instrument with a quantum cascade laser and an antimonide diode laser to measure simultaneously and with high precision seven isotopologues of carbon dioxide and water vapor. Methods and results for determining the effects that limit absorption noise at the level of 5x10(-6) are presented and discussed.

Demonstration of an ethane spectrometer for methane source identification.

Methane is an important greenhouse gas and tropospheric ozone precursor. Simultaneous observation of ethane with methane can help identify specific methane source types. Aerodyne Ethane-Mini spectrometers, employing recently available mid-infrared distributed feedback tunable diode lasers (DFB-TDL), provide 1 s ethane measurements with sub-ppb precision. In this work, an Ethane-Mini spectrometer has been integrated into two mobile sampling platforms, a ground vehicle and a small airplane, and used to measure ethane/methane enhancement ratios downwind of methane sources. Methane emissions with precisely known sources are shown to have ethane/methane enhancement ratios that differ greatly depending on the source type. Large differences between biogenic and thermogenic sources are observed. Variation within thermogenic sources are detected and tabulated. Methane emitters are classified by their expected ethane content. Categories include the following: biogenic (<0.2%), dry gas (1-6%), wet gas (>6%), pipeline grade natural gas (<15%), and processed natural gas liquids (>30%). Regional scale observations in the Dallas/Fort Worth area of Texas show two distinct ethane/methane enhancement ratios bridged by a transitional region. These results demonstrate the usefulness of continuous and fast ethane measurements in experimental studies of methane emissions, particularly in the oil and natural gas sector.