Updated Global Warming Potentials and Radiative Efficiencies of Halocarbons and Other Weak Atmospheric Absorbers.

Human activity has led to increased atmospheric concentrations of many gases, including halocarbons, and may lead to emissions of many more gases. Many of these gases are, on a per molecule basis, powerful greenhouse gases, although at present-day concentrations their climate effect is in the so-called weak limit (i.e., their effect scales linearly with concentration). We published a comprehensive review of the radiative efficiencies (RE) and global warming potentials (GWP) for around 200 such compounds in 2013 (Hodnebrog et al., 2013, https://doi.org/10.1002/rog.20013). Here we present updated RE and GWP values for compounds where experimental infrared absorption spectra are available. Updated numbers are based on a revised "Pinnock curve", which gives RE as a function of wave number, and now also accounts for stratospheric temperature adjustment (Shine & Myhre, 2020, https://doi.org/10.1029/2019MS001951). Further updates include the implementation of around 500 absorption spectra additional to those in the 2013 review and new atmospheric lifetimes from the literature (mainly from WMO (2019)). In total, values for 60 of the compounds previously assessed are based on additional absorption spectra, and 42 compounds have REs which differ by >10% from our previous assessment. New RE calculations are presented for more than 400 compounds in addition to the previously assessed compounds, and GWP calculations are presented for a total of around 250 compounds. Present-day radiative forcing due to halocarbons and other weak absorbers is 0.38 [0.33-0.43] W m-2, compared to 0.36 [0.32-0.40] W m-2 in IPCC AR5 (Myhre et al., 2013, https://doi.org/10.1017/CBO9781107415324.018), which is about 18% of the current CO2 forcing.

An experimental and theoretical study of the gas phase kinetics of atomic chlorine reactions with CH3NH2, (CH3)2NH, and (CH3)3N.

The rate coefficients for the reactions of Cl((2)PJ) with methylamine (R1), dimethylamine (R2) and trimethylamine (R3) have been measured using the laser flash photolysis - resonance fluorescence technique as a function of temperature (274-435 K) and pressure (25-400 Torr N2). The experimental data are well-represented by the following temperature- and pressure-independent rate coefficients (10(10) × k/cm(3) molecule(-1) s(-1)): kR1 = 2.90 ± 0.44, kR2 = 3.89 ± 0.58, kR3 = 3.68 ± 0.55; the uncertainties are estimates of accuracy at the 95% confidence level. Potential energy surfaces (PES) for the reactions have been characterized at the MP2/cc-pVTZ level and improved single point energies of stationary points obtained in CCSD(T)-F12a calculations. The PES for all reactions are characterized by the formation of pre and post reaction complexes and submerged barriers. Rate coefficients for the reactions were calculated as a function of temperature and pressure using a master equation model based on the coupled cluster theory results. The calculated rate coefficients are in good agreement with experiment; the overall rate coefficients are relatively insensitive to variations of the barrier heights within typical chemical accuracy, but the predicted branching ratios vary significantly. The inclusion of tunnelling has no effect.

Gas-phase reactions of OH with methyl amines in the presence or absence of molecular oxygen. An experimental and theoretical study.

The rate coefficients for the reaction of OH with the alkyl amines: methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), and ethylamine (EA) have been determined using the technique of pulsed laser photolysis with detection of OH by laser-induced fluorescence as a function of temperature from 298 K to ∼600 K. The rate coefficients (10(11) × k/cm(3) molecule(-1) s(-1)) at 298 K in nitrogen bath gas (typically 5-25 Torr) are: k(OH+MA) = 1.97 ± 0.11, k(OH+DMA) = 6.27 ± 0.63, k(OH+TMA) = 5.78 ± 0.48, k(OH+EA) = 2.50 ± 0.13. The reactions all show a negative temperature dependence which can be characterized as: k(OH+MA) = (1.889 ± 0.053) × 10(-11)(T/298 K)(-(0.56±0.10)), k(OH+DMA) = (6.39 ± 0.35) × 10(-11)(T/298 K)(-(0.75±0.18)), k(OH+TMA) = (5.73 ± 0.15) × 10(-11)(T/298 K)(-(0.71±0.10)), and k(OH+EA) = (2.54 ± 0.08) × 10(-11)(T/298 K)(-(0.68±0.10)). OH and OD reactions have very similar kinetics. Potential energy surfaces (PES) for the reactions have been characterized at the MP2/aug-cc-pVTZ level and improved single point energies of stationary points obtained in CCSD(T) and CCSD(T*)-F12a calculations. The PES for all reactions are characterized by the formation of pre- and post-reaction complexes and submerged barriers. The calculated rate coefficients are in good agreement with experiment; the overall rate coefficients are relatively insensitive to variations of the barrier heights within typical chemical accuracy, but the branching ratios vary significantly. The rate coefficients for the reactions of OH/OD with MA, DMA, and EA do not vary with added oxygen, but for TMA a significant reduction in the rate coefficient is observed consistent with OH recycling from a chemically activated peroxy radical. OH regeneration is pressure-dependent and is not significant at 298 K and atmospheric pressure, but the efficiency of recycling increases strongly with temperature. The PES for OH recycling have been calculated. There is evidence that the primary process in TMA photolysis at 248 nm is the loss of H atoms.

Raman spectroscopy of the system iron(III)-sulfuric acid-water: an approach to Tinto River's (Spain) hydrogeochemistry.

Acid mine drainage is formed when pyrite (FeS(2)) is exposed and reacts with air and water to form sulfuric acid and dissolved iron. Tinto River (Huelva, Spain) is an example of this phenomenon. In this study, Raman spectroscopy has been used to investigate the speciation of the system iron(III)-sulfuric acid-water as an approach to Tinto River's aqueous solutions. The molalities of sulfuric acid (0.09 mol/kg) and iron(III) (0.01-1.5 mol/kg) were chosen to mimic the concentration of the species in Tinto River waters. Raman spectra of the solutions reveal a strong iron(III)-sulfate inner-sphere interaction through the nu(1) sulfate band at 981 cm(-1) and its shoulder at 1005 cm(-1). Iron(III)-sulfate interaction may also be facilitated by hydrogen bonds and monitored in the Raman spectra through the symmetric stretching band of bisulfate at 1052 cm(-1) and a shoulder at 1040 cm(-1). Other bands in the low-frequency region of the Raman spectra are attributed to the hydrogen-bonded complexes formation as well.

Optical constants of HNO3/H2O and H2SO4/HNO3/H2O at low temperatures in the infrared region.

The complex index of refraction of liquid HNO3/H2O and H2SO4/HNO3/H2O has been obtained at different temperatures and acid concentrations. FT-IR specular reflectance spectra were obtained for 30, 54, and 64 wt % aqueous HNO3 and for four different H2SO4/HNO3/H2O mixtures in the temperature region from 293 to 183 K. The complex index of refraction was obtained from the reflectance spectra with the Kramers-Kronig transformation. The optical constants of the binary and ternary mixtures vary with the acid concentration and the temperature. The results demonstrate that vibrational bands originating from the sulfate species are more sensitive to changes in temperature than the bands originating from vibrations in the nitrate species; only minor changes in the nitrate vibrational bands are observed as the temperature decreases below 248 K.

Follow-up after cervical laminectomy, with special reference to instability and deformity.

Misalignment and instability after cervical laminectomy, performed to treat spondylotic myelopathy, has been described as possible adverse effects. Forty-six consecutively patients on whom laminectomy had been performed in a 4-year period were identified; 7.7 +/- 0.6 years after operation, 11 patients had died and 27 patients were available for follow-up. Postoperative static subluxation was observed in 26% of the patients with an average slip of 3.7 +/- 3.1 mm; 7% had abnormal intervertebral movement displaying 1-2 mm movement from full flexion to full extension. Seventy-four per cent of the patients showed abnormal spinal curvature as judged from radiographs. However, no correlation with outcome was observed. Seventy-four per cent of the patients thought of the result of the operation as either good or fair; objectively, the best long-term effect of the operation was upon arm function. Although some patients develop postural anomaly, laminectomy remains, in terms of instability, a justifiable procedure in the elderly patient with spondylosis.

Effect of scenario and experience on interpretation of mach bands.

The creation of the radiographic illusion known as a mach band at the intersection of two images of differing radiopacities can be misinterpreted as pathosis in certain situations. After reviewing instances where misinterpretation may occur, this study asked 33 fourth-year dental students and 40 dentists to interpret the same radiograph involving a maxillary central incisor under two different hypothetical scenarios: first, in the case of a patient requesting vital bleaching, and second, where a patient has received recent trauma to the mouth. Results showed that dental students are more susceptible than dentists to misinterpreting as a horizontal root fracture (a mach band illusion) what is known to be the junction of alveolar crestal bone and root. Furthermore when presented with a scenario of trauma, both students and dentists are more likely to mistake what is being seen as being a fracture line.

Evaluation of root reinforcement of endodontically treated teeth.

OBJECTIVES: The purpose of this study was to test the root reinforcing capabilities of a glass ionomer sealer and to test whether pretreatment of the instrumented canal to alter or remove the smear layer might enhance the reinforcement. STUDY DESIGN: Ninety single-canaled roots of standardized dimensions were instrumented to International Standards Organization size 45 and were analyzed for resistance to vertical fracture. Six groups were tested (n = 15). RESULTS: No significant difference in fracture resistance was observed between any of the groups. CONCLUSIONS: Under the conditions of this study, reinforcement of endodontically treated mature teeth by placement of adhesive materials in the root was not demonstrated.

Quality of root-end preparations using ultrasonic and rotary instrumentation in cadavers.

Prior investigations have demonstrated dentinal cracking and chipping during ultrasonic preparation of the root-end. This study compared the frequency of cracking and chipping in two groups, cadaver and extracted teeth, using an indirect resin technique. Preparations were performed using either a 33 1/2 inverted cone bur in a high-speed handpiece, or with ultrasonics using a CT-2 tip at either high or low intensity. After replication of the root-end in epoxy resin, all teeth were evaluated for cracking and chipping under scanning electron microscopy. Statistical analysis using a general contingency table or ANOVA with Scheffé post-hoc analysis (p = 0.05) revealed no significant difference between all groups in terms of root-end cracking. In extracted teeth (n = 15), rotary instrumentation produced less chipping than either ultrasonic technique. Varying the intensity was not significant. There was no significant difference between any instrumentation group in cadaver teeth (n = 10) related to the amount of chipping.

Influence of Sub- Versus Top-irrigation and Surfactants in a Recirculating System on Disease Incidence Caused by Phytophthora spp. in Potted Pepper Plants.

Zoospores of Phytophthora capsici spread from inoculated source plants to healthy potted pepper plants located on separate ebb-and-flow benches when the recycled nutrient solution originated from a common reservoir. Amending the recirculating nutrient solution with a surfactant, which selectively kills zoospores, resulted in 100% control of the spread of the pathogen in an ebb-and-flow and a top-irrigated cultural system. Without a surfactant in the recirculating nutrient solution, all plants in an ebb-and-flow cultural system died within 6 weeks. In contrast, all plants in a top-irrigated cultural system died within 2 weeks after inoculation of source plants. These results suggest that the use of recycled irrigation water in an ebb-and-flow cultural system is less conducive to pathogen spread than its use in a top-irrigated cultural system, but may still serve as efficient means of inoculum movement in the absence of control measures.

Comparison of the obturation of lateral canals by six techniques.

The following obturation techniques were compared on their ability to obturate lateral canals in vitro, lateral condensation (LC), continuous wave of condensation (CW), warm vertical condensation (WV), carrier-based thermoplasticized gutta-percha (CB), warm lateral condensation (WL), and vertically condensed high-temperature gutta-percha (HT). A root canal system with lateral canals in the coronal, middle, and apical thirds was prepared in resin blocks. Each block was obturated using each technique (n = 30, 15 each, with and without sealer). The length of gutta-percha and sealer in each of the lateral canals was measured with a measuring microscope and statistically compared. All techniques obturated all three levels of lateral canals with sealer. WV, CB, and CW were able to fill the lateral canals with gutta-percha significantly better when root canal sealer was used. WV, CB, CW, and HT filled the coronal and middle lateral canals significantly better with gutta-percha than LC or WL condensation. CB and CW filled the apical lateral canal significantly better with gutta-percha than HT, WV, WL, or LC.

Palindromic oligonucleotide-directed enzymatic determination of 2'-deoxythymidine 5'-triphosphate and 2'-deoxycytidine 5'-triphosphate in human cells.

A new method is presented for the determination of 2'-deoxythymidine 5'-triphosphate and 2'-deoxycytidine 5'-triphosphate concentrations within human cells based on a DNA polymerase reaction directed by a palindromic oligonucleotide precursor. Two 19-mer oligonucleotide precursors are employed that contain a common 8-mer palindromic sequence followed by a sequence-specific insertion site and a 5'-oligodeoxythymidylate tail. To conduct a measurement, two molecules of the 19-mer oligonucleotide precursor are first annealed to form a pair of symmetrical template-primer addition sites at their 3'-termini that are coded for the analyte of interest, present in limiting amounts. The Klenow fragment of Escherichia coli DNA polymerase I then elongates the template-primer by the addition of two molecules of the complementary deoxyribonucleotide analyte. Following the addition of the analyte molecules, the template-primer is extended with a 10-mer oligo(dA) tail in the presence of excess dATP and the Klenow fragment. The result is a 30-mer palindromic oligonucleotide that can be separated from any remaining 19-mer precursor and quantified by paired-ion HPLC using UV detection. Since the molar extinction coefficient of the 30-mer palindromic oligonucleotide is much larger than that of the nucleotide analyte alone, the UV signal is markedly enhanced, thereby increasing sensitivity. Details describing this method and the application of it to measure these analytes in as few as 2.5 x 10(6) human cells are presented.

Treatment of shunt-related cerebral ventriculitis due to Corynebacterium jeikeium with vancomycin administered intraventricularly. Case report.

A 52-year-old female with subarachnoid haemorrhage and hydrocephalus was treated with external and later internal drainage. She developed ventriculoperitoneal shunt-related ventriculitis caused by Corynebacterium jeikeium. The infection was unsuccessfully treated with intravenous vancomycin. It was controlled only after shunt removal and administration of intraventricular vancomycin as well as systemic vancomycin, rifampicin and fusidic acid. A review of the literature confirmed our experience that vancomycin given intraventricularly is well tolerated and doses can be individualized by measuring vancomycin levels in cerebrospinal fluid.

[Intensive back exercises 5 weeks after surgery of lumbar disk prolapse. A prospective, randomized multicenter trial with a historical control group]. / Intensiv rygtraening fem uger efter lumbal diskusprolapsoperation. En prospektiv, randomiseret multicenterundersøgelse med historisk kontrolgruppe.

An intensive, dynamic rehabilitation program applied to patients who had undergone first time lumbar discectomy was evaluated in a multicentre, clinical trial. Ninety-six patients between 18 and 70 years of age who had been operated within the period September 1989 to May 1990 at the Department of Neurosurgery, Copenhagen County Hospital, Glostrup were consecutively randomized into one of two rehabilitation programs: a) traditional mild, general mobility-improving exercises within pain limits; or b) intensive dynamic back extension and abdominal exercises without low back pain being the limiting factor. Both groups underwent 14 hours of treatment over a period of six weeks, starting five weeks after surgery. Seventy-six patients operated within the period January 1989 to September 1989 formed the historical control group. The results at follow-up at 26 weeks favoured intensive exercises with regard to the patients disability-index and working capabilities. The results are statistically significant. After one year a trend favouring intensive exercises can be observed. No differences in pain or objective measurements were found. A rehabilitation program using intensive exercises without back pain being the limiting factor appears to give the patients increased behavioural support, resulting in improvements in work capacity and reduction in patients' self-rated disability.

Brain biopsy in AIDS. Diagnostic value and consequence.

Nineteen male patients with AIDS were investigated by biopsy of brain lesions. Six patients had progressive multiple leucoencephalopathy and no specific treatment was given. Toxoplasmosis (two patients), bacterial abscesses (two cases), viral encephalitis (two patients) and only gliosis (two cases) accounted for almost half of the cases. A fungal infection, a lymphoma and a sarcoma-like tumour were found in three patients. In two patients the biopsy was not diagnostic: one had only necrosis and one had normal findings. The biopsy findings gave reason for modifying the treatment in only three cases. The mean survival rate was relatively short, only 76 days with a range from 1 to 1041 days. Two patients were in a very bad clinical condition at the time of biopsy and one died of a haemorrhagic complication due to the biopsy. In ten cases an autopsy was carried out. In five cases there was agreement between the biopsy and autopsy findings. In the other five cases the autopsy findings differed widely. In our experience we can recommend cerebral biopsy in patients with AIDS only after treatment for toxoplasmosis and mainly to estimate the prognosis.

Photocarcinogenesis is retarded by a partly photodegraded solution of para-aminobenzoic acid.

A solution of para-aminobenzoic acid (PABA) was exposed to ultraviolet (UV) radiation emitted from a Philips TL 40 W/12 sunlamp and the degree of photodegradation following an exposure of 27 J/cm2 was estimated to be approximately 40%. The formation of the photoproducts was confirmed by mass spectroscopy and UV spectroscopy. The solution was painted on the backs of hairless light-pigmented mice prior to daily UV irradiation by the above sunlamp, and this procedure was continued for 30 weeks. The preirradiated solution of PABA significantly retarded the tumor induction time and reduced significantly the number of squamous cell carcinomas compared with nonprotected controls. This tumor-retarding ability did not differ significantly from the effect achieved when using nonirradiated PABA.

Structure-activity relationship of the preservation and restoration of glucocorticoid receptors in rat hepatocytes and rat liver homogenates by sulfhydryl, phosphorothioate and disulfide compounds.

The purpose of this work was to examine whether the ability of dithiothreitol to preserve the steroid-binding capacity of glucocorticoid receptors in subcellular preparations is specific or a general property of sulfhydryl compounds and selected phosphorothioate and disulfide derivatives. A further goal was to see if this effect could be demonstrated in intact cells. The ability to preserve the steroid-binding capacity of the glucocorticoid receptor is not a universal property of all sulfhydryl compounds since many of the compounds tested were inactive. The steroid-binding capacity of the glucocorticoid receptor of the 100,000 g supernatant of rat liver homogenate is preserved/restored by sulfhydryl compounds containing a mercaptoethylamine or mercaptopropylamine subunit. However, small changes in the structure of the sulfhydryl compound such as the rearrangement of a methylene group significantly alter its effectiveness. All of the phosphorothioates examined are derivatives of active sulfhydryl compounds and are effective in preserving steroid-binding. The extent of metabolism of the phosphorothioates and their failure to restore steroid-binding capacity after short-time exposure to receptor preparations are consistent with the sulfhydryl form being the active form of the phosphorothioates. S-2-(3-Amino-propylamino)ethylphosphorothioic acid (WR 2721) preserved steroid-binding capacity in isolated intact rat hepatocytes down to 25 microM demonstrating that concentrations obtainable in whole animals are effective with intact cells. Disulfide derivatives of active sulfhydryl compounds are either immediately toxic or ineffective except for 1,18-diamino-6,13-diaza-9,10-dithiaoctadecane (WR 149,024) which is more effective than its corresponding sulfhydryl. The demonstration that some sulfhydryl-forming compounds preserve the steroid-binding capacity of glucocorticoid receptors in intact cells at potentially physiologically obtainable concentrations suggests a potential role for these or similar compounds to bolster the efficacy of conventional glucocorticoid therapy.

Measurements of the photodegradation of PABA and some PABA derivatives.

The photodegradation of 4-aminobenzoic acid, 2-ethylhexyl N,N-dimethyl 4-aminobenzoate (Escalol 507) and 1-glyceryl 4-aminobenzoate (Escalol 106), resulting from irradiation by sun lamps, was examined by UV spectroscopy. 2-ethylhexyl N,N-dimethyl 4-aminobenzoate showed the longest half-life, indicating the highest photostability.