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The fluctuating hydrogen bridge bonded network of liquid water at ambient conditions entails a varied ensemble of the underlying constituting H2O molecular moieties. This is mirrored in a manifold of the H2O molecular potentials. Subnatural line width resonant inelastic X-ray scattering allowed us to quantify the manifold of molecular potential energy surfaces along the H2O symmetric normal mode and the local asymmetric O-H bond coordinate up to 1 and 1.5 angstrom, respectively. The comparison of the single H2O molecular potentials and spectroscopic signatures with the ambient conditions liquid phase H2O molecular potentials is done on various levels. In the gas phase, first principles, Morse potentials, and stepwise harmonic potential reconstruction have been employed and benchmarked. In the liquid phase the determination of the potential energy manifold along the local asymmetric O-H bond coordinate from resonant inelastic X-ray scattering via the bound state oxygen ls to 4a(1) resonance is treated within these frameworks. The potential energy surface manifold along the symmetric stretch from resonant inelastic X-ray scattering via the oxygen 1 s to 2b(2) resonance is based on stepwise harmonic reconstruction. We find in liquid water at ambient conditions H2O molecular potentials ranging from the weak interaction limit to strongly distorted potentials which are put into perspective to established parameters, i.e., intermolecular O-H, H-H, and O-O correlation lengths from neutron scattering.
Multi-year index-based insurance for adapting Water Utility Companies to hydrological drought
(2020)
The sustainability of water utility companies is threatened by non-stationary drivers, such as climate and anthropogenic changes. To cope with potential economic losses, instruments such as insurance are useful for planning scenarios and mitigating impacts, but data limitations and risk uncertainties affect premium estimation and, consequently, business sustainability. This research estimated the possible economic impacts of business interruption to the Sao Paulo Water Utility Company derived from hydrological drought and how this could be mitigated with an insurance scheme. Multi-year insurance (MYI) was proposed through a set of "change" drivers: the climate driver, through forcing the water evaluation and planning system (WEAP) hydrological tool; the anthropogenic driver, through water demand projections; and the economic driver, associated with recent water price policies adopted by the utility company during water scarcity periods. In our study case, the evaluated indices showed that MYI contracts that cover only longer droughts, regardless of the magnitude, offer better financial performance than contracts that cover all events (in terms of drought duration). Moreover, through MYI contracts, we demonstrate solvency for the insurance fund in the long term and an annual average actuarially fair premium close to the total expected revenue reduction.
Background Recent shoulder injury prevention programs have utilized resistance exercises combined with different forms of instability, with the goal of eliciting functional adaptations and thereby reducing the risk of injury. However, it is still unknown how an unstable weight mass (UWM) affects the muscular activity of the shoulder stabilizers. Aim of the study was to assess neuromuscular activity of dynamic shoulder stabilizers under four conditions of stable and UWM during three shoulder exercises. It was hypothesized that a combined condition of weight with UWM would elicit greater activation due to the increased stabilization demand. Methods Sixteen participants (7 m/9 f) were included in this cross-sectional study and prepared with an EMG-setup for the: Mm. upper/lower trapezius (U.TA/L.TA), lateral deltoid (DE), latissimus dorsi (LD), serratus anterior (SA) and pectoralis major (PE). A maximal voluntary isometric contraction test (MVIC; 5 s.) was performed on an isokinetic dynamometer. Next, internal/external rotation (In/Ex), abduction/adduction (Ab/Ad) and diagonal flexion/extension (F/E) exercises (5 reps.) were performed with four custom-made-pipes representing different exercise conditions. First, the empty-pipe (P; 0.5 kg) and then, randomly ordered, water-filled-pipe (PW; 1 kg), weight-pipe (PG; 4.5 kg) and weight + water-filled-pipe (PWG; 4.5 kg), while EMG was recorded. Raw root-mean-square values (RMS) were normalized to MVIC (%MVIC). Differences between conditions for RMS%MVIC, scapular stabilizer (SR: U.TA/L.TA; U.TA/SA) and contraction (CR: concentric/eccentric) ratios were analyzed (paired t-test; p <= 0.05; Bonferroni adjusted alpha = 0.008). Results PWG showed significantly greater muscle activity for all exercises and all muscles except for PE compared to P and PW. Condition PG elicited muscular activity comparable to PWG (p > 0.008) with significantly lower activation of L.TA and SA in the In/Ex rotation. The SR ratio was significantly higher in PWG compared to P and PW. No significant differences were found for the CR ratio in all exercises and for all muscles. Conclusion Higher weight generated greater muscle activation whereas an UWM raised the neuromuscular activity, increasing the stabilization demands. Especially in the In/Ex rotation, an UWM increased the RMS%MVIC and SR ratio. This might improve training effects in shoulder prevention and rehabilitation programs.
Groundwater levels are monitored by environmental agencies to support the sustainable use of groundwater resources. For this purpose continuous and spatially comprehensive monitoring in high spatial and temporal resolution is desired. This leads to large datasets that have to be checked for quality and analysed to distinguish local anthropogenic influences from natural variability of the groundwater level dynamics at each well. Both technical problems with the measurements as well as local anthropogenic influences can lead to local anomalies in the hydrographs. We suggest a fast and efficient screening method for the identification of well-specific peculiarities in hydrographs of groundwater head monitoring networks. The only information required is a set of time series of groundwater heads all measured at the same instants of time. For each well of the monitoring network a reference hydrograph is calculated, describing expected "normal" behaviour at the respective well as is typical for the monitored region. The reference hydrograph is calculated by multiple linear regression of the observed hydrograph with the "stable" principal components (PCs) of a principal component analysis of all groundwater head series of the network as predictor variables. The stable PCs are those PCs which were found in a random subsampling procedure to be rather insensitive to the specific selection of the analysed observation wells, i.e. complete series, and to the specific selection of measurement dates. Hence they can be considered to be representative for the monitored region in the respective period. The residuals of the reference hydrograph describe local deviations from the normal behaviour. Peculiarities in the residuals allow the data to be checked for measurement errors and the wells with a possible anthropogenic influence to be identified. The approach was tested with 141 groundwater head time series from the state authority groundwater monitoring network in northeastern Germany covering the period from 1993 to 2013 at an approximately weekly frequency of measurement.
Carbon adsorbents from spent coffee for removal of methylene blue and methyl orange from water
(2021)
Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed.
Visible-Light-Mediated Photodynamic Water Disinfection @ Bimetallic-Doped Hybrid Clay Nanocomposites
(2019)
This study reports a new class of photocatalytic hybrid clay nanocomposites prepared from low-cost sources (kaolinite clay and Carica papaya seeds) doped with Zn and Cu salts via a solvothermal process. X-ray diffraction analysis suggests that Cu-doping and Cu/Zn-doping introduce new phases into the crystalline structure of Kaolinite clay, which is linked to the reduced band gap of kaolinite from typically between 4.9 and 8.2 eV to 2.69 eV for Cu-doped and 1.5 eV for Cu/Zn hybrid clay nanocomposites (Nisar, J.; Arhammar, C.; Jamstorp, E.; Ahuja, R. Phys. Rev. B 2011, 84, 075120). In the presence of solar light irradiation, Cu- and Cu/Zn-doped nanocomposites facilitate the electron hole pair separation. This promotes the generation of singlet oxygen which in turn improves the water disinfection efficiencies of these novel nanocomposite materials. The nanocomposite materials were further characterized using high-resolution scanning electron microscopy, fluorimetry, therrnogravimetric analysis, and Raman spectroscopy. The breakthrough times of the nanocomposites for a fixed bed mode of disinfection of water contaminated with 2.32 x 10(7) cfu/mL E. coli ATCC 25922 under solar light irradiation are 25 h for Zn-doped, 30 h for Cu-doped, and 35 h for Cu/Zn-doped nanocomposites. In the presence of multidrug and multimetal resistant strains of E. coli, the breakthrough time decreases significantly. Zn-only doped nanocomposites are not photocatalytically active. In the absence of light, the nanocomposites are still effective in decontaminating water, although less efficient than under solar light irradiation. Electrostatic interaction, metal toxicity, and release of singlet oxygen (only in the Cu-doped and Cu/Zn-doped nanocomposites) are the three disinfection mechanisms by which these nanocomposites disinfect water. A regrowth study indicates the absence of any living E. coli cells in treated water even after 4 days. These data and the long hydraulic times (under gravity) exhibited by these nanocomposites during photodisinfection of water indicate an unusually high potential of these nanocomposites as efficient, affordable, and sustainable point-of-use systems for the disinfection of water in developing countries.
Large-scale commercial cropping of soybeans expanded in the tropical Amazon and Cerrado biomes of Brazil after 1990. More recently, cropping intensified from single-cropping of soybeans to double-cropping of soybeans with corn or cotton. Cropland expansion and intensification, and the accompanying use of mineral fertilizers, raise concerns about whether nutrient runoff and impacts to surface waters will be similar to those experienced in commercial cropland regions at temperate latitudes. We quantified water infiltration through soils, water yield, and streamwater chemistry in watersheds draining native tropical forest and single-and double-cropped areas on the level, deep, highly weathered soils where cropland expansion and intensification typically occurs. Although water yield increased four-fold from croplands, streamwater chemistry remained largely unchanged. Soil characteristics exerted important control over the movement of nitrogen (N) and phosphorus (P) into streams. High soil infiltration rates prevented surface erosion and movement of particulate P, while P fixation in surface soils restricted P movement to deeper soil layers. Nitrogen retention in deep soils, likely by anion exchange, also appeared to limit N leaching and export in streamwater from both single-and double-cropped watersheds that received nitrogen fertilizer. These mechanisms led to lower streamwater P and N concentrations and lower watershed N and P export than would be expected, based on studies from temperate croplands with similar cropping and fertilizer application practices.
Picosecond X-ray absorption spectroscopy (XAS) is used to investigate the electronic and structural dynamics initiated by plasmon excitation of 1.8 nm diameter Au nanoparticles (NPs) functionalised with 1-hexanethiol. We show that 100 ps after photoexcitation the transient XAS spectrum is consistent with an 8% expansion of the Au–Au bond length and a large increase in disorder associated with melting of the NPs. Recovery of the ground state occurs with a time constant of ∼1.8 ns, arising from thermalisation with the environment. Simulations reveal that the transient spectrum exhibits no signature of charge separation at 100 ps and allows us to estimate an upper limit for the quantum yield (QY) of this process to be <0.1.