SciCombinator

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Concept: Hydrogen chloride

28

Both nitrate and pentachlorophenol (PCP) are familiar pollutants in aqueous environment. This research is focused on the simultaneous removal of nitrate and PCP from simulated contaminated groundwater using a laboratory-scale denitrification reactor packed with corncob as both carbon source and biofilm support. The reactor could be started up readily, and the removal efficiencies of nitrate and PCP reached up to approximately 98 % and 40-45 % when their initial concentrations were 50 mg N/L and 5 mg/L, respectively, after 15-day continuous operation at 10 h of hydraulic retention time (HRT) and 25 °C. Approximately 91 % of PCP removal efficiency was achieved, with 2.47 mg/L of chloride ion release at 24 h of HRT. Eighty-two percent of chlorine in PCP removed was ionized. The productions of 3-chlorophenol and phenol and chloride ion release indicate that the reductive dechlorination reaction is a major degradation pathway of PCP under the experimental conditions.

Concepts: Concentration, Chemistry, Water pollution, Sodium chloride, Ion, Chlorine, Chloride, Hydrogen chloride

17

In June 2015, personnel from California’s Contra Costa Health Services Environmental Health and Hazardous Materials (hazmat) divisions were alerted to a possible chemical release at a swimming pool in an outdoor municipal water park. Approximately 50 bathers were in the pool when symptoms began; 34 (68%) experienced vomiting, coughing, or eye irritation. Among these persons, 17 (50%) were treated at the scene by Contra Costa’s Emergency Medical Services (EMS) and released, and 17 (50%) were transported to local emergency departments; five patients also were evaluated later at an emergency department or by a primary medical provider. Environmental staff members determined that a chemical controller malfunction had allowed sodium hypochlorite and muriatic acid (hydrochloric acid) solutions to be injected into the main pool recirculation line while the recirculation pump was off; when the main recirculation pump was restarted, toxic chlorine gas (generated by the reaction of concentrated sodium hypochlorite and muriatic acid) was released into the pool. A review of 2008-2015 California pesticide exposure records identified eight additional such instances of toxic chlorine gas releases at public aquatic venues caused by equipment failure or human error that sickened 156 persons. Chemical exposures at public aquatic venues can be prevented by proper handling, storage, and monitoring of pool chemicals; appropriate equipment operation and maintenance; training of pool operators and staff members on pool chemical safety; and reporting of chemical exposures.

Concepts: Hydrogen, Sodium chloride, Chlorine, Hypochlorous acid, Hydrogen chloride, Hydrochloric acid, Swimming pool, Sodium carbonate

11

Ingestion of contaminated soil is one potential internal exposure pathway in areas contaminated by the Fukushima Daiichi Nuclear Power Plant accident. Doses from this pathway can be overestimated if the availability of radioactive nuclides in soils for the gastrointestinal tract is not considered. The concept of bioaccessibility has been adopted to evaluate this availability based on in vitro tests. This study evaluated the bioaccessibility of radioactive cesium from soils via the physiologically-based extraction test (PBET) and the extractability of those via an extraction test with 1 mol/L of hydrochloric acid (HCl). The bioaccessibility obtained in the PBET was 5.3% ± 1%, and the extractability in the tests with HCl was 16% ± 3%. The bioaccessibility was strongly correlated with the extractability. This result indicates the possibility that the extractability in HCl can be used as a good predictor of the bioaccessibility with PBET. In addition, we assessed the doses to children from the ingestion of soil via hand-to-mouth activity based on our PBET results using a probabilistic approach considering the spatial distribution of radioactive cesium in Date City in Fukushima Prefecture and the interindividual differences in the surveyed amounts of soil ingestion in Japan. The results of this assessment indicate that even if children were to routinely ingest a large amount of soil with relatively high contamination, the radiation doses from this pathway are negligible compared with doses from external exposure owing to deposited radionuclides in Fukushima Prefecture.

Concepts: Chernobyl disaster, Digestive system, Chlorine, Nuclear power, Hydrogen chloride, Hydrochloric acid, Fukushima Prefecture, Tōhoku region

4

Trichloroethylene (TCE) is a widespread environmental pollutant common in groundwater plumes associated with industrial manufacturing areas. We had previously isolated and characterized a natural bacterial endophyte, Enterobacter sp. strain PDN3, of poplar trees, that rapidly metabolizes TCE, releasing chloride ion. We now report findings from a successful three-year field trial of endophyte-assisted phytoremediation on the Middlefield-Ellis-Whisman Superfund Study Area TCE plume in the Silicon Valley of California. The inoculated poplar trees exhibited increased growth and reduced TCE phytotoxic effects with a 32% increase in trunk diameter compared to mock-inoculated control poplar trees. The inoculated trees excreted 50% more chloride ion into the rhizosphere, indicative of increased TCE metabolism in planta. Data from tree core analysis of the tree tissues provided further supporting evidence of the enhanced rate of degradation of the chlorinated solvents in the inoculated trees. Test well groundwater analyses demonstrated a marked decrease in concentration of TCE and its derivatives from the tree-associated groundwater plume. The concentration of TCE decreased from 300 µg/L upstream of the planted area to less than 5 µg/L downstream of the planted area. TCE derivatives were similarly removed with cis-1,2-dichloroethene decreasing from 160 µg/L to less than 5 µg/L and trans-1,2-dichloroethene decreasing from 3.1 µg/L to less than 0.5 µg/L downstream of the planted trees. 1,1-dichloroethene and vinyl chloride both decreased from 6.8 and 0.77 µg/L, respectively, to below the reporting limit of 0.5 µg/L providing strong evidence of the ability of the endophytic inoculated trees to effectively remove TCE from affected groundwater. The combination of native pollutant-degrading endophytic bacteria and fast-growing poplar tree systems offers a readily deployable, cost-effective approach for the degradation of TCE, and may help mitigate potential transfer up the food chain, volatilization to the atmosphere, as well as direct phytotoxic impacts to plants used in this type of phytoremediation.

Concepts: Plant, Ion, Chlorine, Trees, Hydrogen chloride, Endophyte, Hydrochloric acid, Love Canal

1

The synthesis of carboxylic acid derivatives from unsaturated hydrocarbons is an important process for the preparation of polymers, pharmaceuticals, cosmetics and agrochemicals. Despite its industrial relevance, the traditional Reppe-type carbonylation reaction using pressurized CO is of limited applicability to laboratory-scale synthesis because of: (1) the safety hazards associated with the use of CO, (2) the need for special equipment to handle pressurized gas, (3) the low reactivity of several relevant nucleophiles and (4) the necessity to employ different, often tailor-made, catalytic systems for each nucleophile. Herein we demonstrate that a shuttle-catalysis approach enables a CO- and HCl-free transfer process between an inexpensive reagent, butyryl chloride, and a wide range of unsaturated substrates to access the corresponding acid chlorides in good yields. This new transformation provides access to a broad range of carbonyl-containing products through the in situ transformation of the reactive acid chloride intermediate. In a broader context, this work demonstrates that isodesmic shuttle-catalysis reactions can unlock elusive catalytic reactions.

Concepts: Alcohol, Amine, Chemical reaction, Functional group, Hydrogen, Catalysis, Carboxylic acid, Hydrogen chloride

1

The pressure-temperature phase diagram of ice displays a perplexing variety of structurally distinct phases. In the century-long history of scientific research on ice, the proton-ordered ice phases numbered XIII through XV were discovered only recently. Despite considerable effort, none of the transitions leading from the low-temperature ordered ices VIII, IX, XI, XIII, XIV and XV to their high-temperature disordered counterparts were experimentally found to display the full Pauling entropy. Here we report calorimetric measurements on suitably high-pressure-treated, hydrogen chloride-doped ice XIV that demonstrate just this at the transition to ice XII. Dielectric spectroscopy on undoped and on variously doped ice XII crystals reveals that addition of hydrogen chloride, the agent triggering complete proton order in ice XIV, enhances the precursor dynamics strongest. These discoveries provide new insights into the puzzling observation that different dopants trigger the formation of different proton-ordered ice phases.

Concepts: Crystal, Hydrogen, Ice, Phase, Chlorine, Triple point, Hydrogen chloride, Hydrochloric acid

0

Biogas from biological treatments and from the waste degradation in landfills generally contains a wide range of trace impurities (e.g., sulphur compounds, siloxanes, halogens, tar compounds, etc.). This paper describes an experimental analysis performed with SOFC single cells fed by a synthetic gas polluted by H2S, HCl, D4 and a mixture of H2S + C2Cl4. The aim is to detect the threshold tolerance limit on different cell performance parameters. Results show how: hydrogen sulphide has a strong impact on the polarization losses due to the nickel sulphide formation on the electrode that causes a mass transfer resistance. Hydrogen chloride particularly limited the electrochemical processes. Octamethylcyclotetrasiloxane (D4) showed a high impact on SOFC performance even at ultra-low level (78-178 ppb(v)) as a consequence of the formation of silicon dioxide covering the anode porous sites. Sulphur added to C2Cl4, accelerated the deterioration of SOFC performance. In addition, current density variations and operating temperature are studied during sulphur poisoning. An opposite behaviour on SOFC performance was revealed by operating temperature and current density.

Concepts: Oxygen, Density, Sulfur, Hydrogen sulfide, Chlorine, Natural gas, Hydrogen chloride, Hydrochloric acid

0

The first examples of amino-substituted fused-ring metallabenzenes, the cationic iridabenzofuran [Ir(C7H4O{NH2-2}{OMe-7})(CO)(PPh3)2][O3SCF3] (5) and neutral analogue Ir(C7H4{NH2-2}{OMe-7})Cl(PPh3)2 (6), can be prepared by reduction of the corresponding nitro-substituted iridabenzofurans with zinc and concentrated hydrochloric acid. N-functionalised derivatives of 5 and 6 are formed through alkylation, sulfonylation or acylation. Thus, consecutive treatments with methyl triflate and base gives the corresponding trimethylammonium-substituted iridabenzofurans while sulfonamide derivatives are formed with p-toluenesulfonyl chloride. N-acylation of 5 or 6 with acid chlorides, however, selectively form either amide or imide products depending on the charge on the metal and the steric size of the acid chloride. Cationic 5 gives amide substituted products regardless of the conditions whereas neutral 6 rapidly undergoes di-N-acylation with excess benzoyl chloride under mild conditions to give the imide-substituted product Ir(C7H4O{N[C(O)Ph]2-2}{OMe-7})Cl(PPh3)2 (13). Selective mono-acylation of 6 can be achieved with one equivalent of benzoyl chloride or with excess of the sterically congested pivaloyl chloride.

Concepts: Amine, Sodium chloride, Carbonyl, Carboxylic acid, Chlorine, Chloride, Hydrogen chloride, Hydrochloric acid

0

High contact resistance between silver nanowires (AgNWs) is a key issue in widespread application of AgNW flexible transparent conductive films as a promising candidate to replace the brittle and expensive indium tin oxide. A facile, room-temperature nanowelding method of an AgNW network triggered by hydrogen chloride (HCl) vapor is demonstrated to reduce the sheet resistance of the AgNW network. Under the visible light, O2 and HCl vapor serving as an etching couple induced silver atoms to be transferred from the bottom AgNW at the junction to the top one, and then, these silver atoms epitaxially recrystallized at the contact position with the lattice of the top AgNW as the template, ultimately resulting in the coalescence of the junction between AgNWs. Polydimethylsiloxane (PDMS) was spin-coated onto the HCl-vapor-treated (HVT) AgNW network on the polyethylene terephthalate substrate to fabricate PDMS/HVT AgNW films. The fabricated film with low sheet resistance and high transmittance retained its conductivity after 4000 bending cycles. Furthermore, excellent heating performance, electromagnetic interference shielding effectiveness, and foldability were obtained in the PDMS/HVT AgNW film. Thus, the role of the simple nanowelding process is evident in enhancing the performance of AgNW transparent conductive films for emerging soft optoelectronic applications.

Concepts: Hydrogen, Aluminium, Ion, Nanowire, Solar cell, Chlorine, Hydrogen chloride, Hydrochloric acid

0

A calibration matrix has been developed and successfully applied to quantify actives in Children’s Dimetapp®, a cough mixture whose active components suffer from heavy spectral interference. High-performance liquid chromatography/photodiode array instrument was used to identify the actives and any other UV-detectable excipients that might contribute to interferences. The instrument was also used to obtain reference data on the actives, instead of relying on the manufacturer’s claims. Principal component analysis was used during the developmental stages of the calibration matrix to highlight any mismatch between the calibration and sample spectra, making certain that “apples” were not compared with “oranges”. The prediction model was finally calculated using target factor analysis and partial least squares regression. In addition to the actives in Children’s Dimetapp® (brompheniramine maleate, phenylephrine hydrogen chloride, and dextromethorphan hydrogen bromide), sodium benzoate was identified as the major and FD&C Blue #1, FD&C Red #40, and methyl anthranilate as minor spectral interferences. Model predictions were compared before and after the interferences were included into the calibration matrix. Before including interferences, the following results were obtained: brompheniramine maleate=481.3mgL(-1)±134% RE; phenylephrine hydrogen chloride=1041mgL(-1)±107% RE; dextromethorphan hydrogen bromide=1571mgL(-1)±107% RE, where % RE=percent relative error based on the reference HPLC data. After including interferences, the results were as follows: brompheniramine maleate=196.3mgL(-1)±4.4% RE; phenylephrine hydrogen chloride=501.3mgL(-1)±0.10% RE; dextromethorphan hydrogen bromide=998.7mgL(-1)±1.6% RE as detailed in Table 6.

Concepts: Regression analysis, Hydrogen, Factor analysis, Principal component analysis, Chlorine, Least squares, Singular value decomposition, Hydrogen chloride