Association of a polynuclear iron-sulfur center with a mutant FNR protein enhances DNA binding.

In the facultative anaerobe Escherichia coli, the transcription factor FNR (fumarate nitrate reduction) regulates gene expression in response to oxygen deprivation. To investigate how the activity of FNR is regulated by oxygen availability, two mutant proteins, DA154 and LH28-DA154, which have enhanced in vivo activity in the presence of oxygen, were purified and compared. Unlike other previously examined FNR preparations, the absorption spectrum of LH28-DA154 had two maxima at 324 nm and 419 nm, typical of iron-sulfur (Fe-S)-containing proteins. Consistent with these data, metal analysis showed that only the LH28-DA154 protein contained a significant amount of iron and acid-labile sulfide, and, by low temperature EPR spectroscopy, a signal typical of a [3Fe-4S]+ cluster was detected. The LH28-DA154 protein that contained the Fe-S cluster also contained a higher proportion of dimers and had a 3- to 4-fold higher apparent affinity for the target DNA than the DA154 protein. In agreement with this, we found that when the LH28-DA154 protein was treated with an iron chelator (alpha,alpha'-dipyridyl), it lost its characteristic absorption and the apparent affinity for DNA was reduced 6-fold. However, increased DNA binding and the characteristic absorption spectrum could be restored by in vitro reconstitution of the Fe-S center. DNA binding of the LH28-DA154 protein was also affected by the redox state of the Fe-S center, since protein exposed to oxygen bound 1/10th as much DNA as the protein reduced anaerobically with dithionite. The observation that DNA binding is enhanced when the Fe-S center is reduced indicates that the redox state of the Fe-S center affects the DNA-binding activity of this protein and suggests a possible mechanism for regulation of the wild-type protein.

Sulfur resistance of Pt-W catalysts

The sulfur resistance of low-loaded monometallic Pt catalysts and bimetallic Pt-W catalysts during the partial selective hydrogenation of styrene, a model compound of Pygas streams, was studied. The effect of metal impregnation sequence on the activity and selectivity was also evaluated. Catalysts were characterized by ICP, TPR, XRD, and XPS techniques. Catalytic tests with sulfur-free and sulfur-doped feeds were performed. All catalysts showed high selectivities (>98%) to ethylbenzene. Activity differences between the catalysts were mainly attributed to electronic effects due to the presence of different electron-rich species of Pt0 and electron-deficient species of Ptδ+. Pt0 promotes the cleavage of H2 while Ptδ+ the adsorption of styrene. The catalyst successively impregnated with W and Pt (WPt/Al) was more active and sulfur resistant than the catalyst prepared with an inverse impregnation order (PtW/Al). The higher poison resistance of WPt/Al was attributed to both steric and electronic effects.

Carbon-, sulfur-, and phosphorus-based charge transfer reactions in inductively coupled plasma–atomic emission spectrometry

In this work, the influence of carbon-, sulfur-, and phosphorus-based charge transfer reactions on the emission signal of 34 elements (Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, I, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb, Se, Sr, Te, and Zn) in axially viewed inductively coupled plasma–atomic emission spectrometry has been investigated. To this end, atomic and ionic emission signals for diluted glycerol, sulfuric acid, and phosphoric acid solutions were registered and results were compared to those obtained for a 1% w w− 1 nitric acid solution. Experimental results show that the emission intensities of As, Se, and Te atomic lines are enhanced by charge transfer from carbon, sulfur, and phosphorus ions. Iodine and P atomic emission is enhanced by carbon- and sulfur-based charge transfer whereas the Hg atomic emission signal is enhanced only by carbon. Though signal enhancement due to charge transfer reactions is also expected for ionic emission lines of the above-mentioned elements, no experimental evidence has been found with the exception of Hg ionic lines operating carbon solutions. The effect of carbon, sulfur, and phosphorus charge transfer reactions on atomic emission depends on (i) wavelength characteristics. In general, signal enhancement is more pronounced for electronic transitions involving the highest upper energy levels; (ii) plasma experimental conditions. The use of robust conditions (i.e. high r.f. power and lower nebulizer gas flow rates) improves carbon, sulfur, and phosphorus ionization in the plasma and, hence, signal enhancement; and (iii) the presence of other concomitants (e.g. K or Ca). Easily ionizable elements reduce ionization in the plasma and consequently reduce signal enhancement due to charge transfer reactions.

Sulfur-isotope analyses of gypsium samples from the Southeast Greenland margin, southern Alaska and Gulf of Alaska (Table 1)

Gypsum grains were identified in Miocene-Pleistocene sediment cores from two deep-water ODP sites, Site 918 off the SE Greenland margin and Site 887 in the Gulf of Alaska, and in Holocene sediment cores from shallow-water localities in Disenchantment Bay and Muir Inlet in southern Alaska. Although initial morphologic and textural observations suggested a complex system in which the gypsum may have had more than one origin, quantitative sulfur isotope analyses of the gypsum provide evidence of its detrital nature. d34S values in gypsum from southern Alaska range between +0.0 and +7.1 per mil. Gypsum has d34S values between -27.1 and -27.5 per mil in the Gulf of Alaska and values between -28.5 and +0.2 per mil off the SE Greenland margin. All of these isotopic signatures are too highly depleted in d34S to have precipitated from seawater, present or past. In addition there is no significant change in d34S values for gypsum crystals with differing physical characteristics (abraded vs. unabraded) from the same stratigraphic horizon, suggesting all the gypsum is detrital regardless of the degree of abrasion. The isotopic and physical evidence, in combination with the onshore geology the environmental setting, and site characteristics of the gypsum-bearing marine localities, lead us to propose that the ultimate source of the gypsum is precipitation from freeze-induced terrestrial sediment or soil brines. Furthermore the combined evidence suggests that the subsequent occurrence of gypsum in glacimarine sediments results from ice-rafting (by icebergs or sea ice) of the frozen regolith and/or, in the proximal glacimarine setting of southern Alaska, very rapid burial via turbidity currents.

Sulfur isotope rations in oceanic basement samples

Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

(Table 2) Isotopic composition of pyrite sulfur in bottom sediments and carbonate nodules from the Gulf of California at Station DM9-666

New data on phosphorites collected by dredging and trawling at depths from 2700 to 520 m in the open Atlantic Ocean (i.e. outside of the shelf and the continental slope) are reported. Aphanitic, granular, brecciated, and conglomerate-like types are distinguished among the phosphorites. A comparison of the studied phosphorites with ones from the Atlantic shelf of Africa and from seamounts of other oceans is made.

Net community production, Thorium-234 activity and particle flux during the Southern Ocean iron fertilization experiment LOHAFEX

A closed eddy core in the Subantarctic Atlantic Ocean was fertilized twice with two tons of iron (as FeSO4), and the 300 km**2 fertilized patch was studied for 39 days to test whether fertilization enhances downward particle flux into the deep ocean. Chlorophyll a and primary productivity doubled after fertilization, and photosynthetic quantum yield (FV/FM) increased from 0.33 to >0.40. Silicic acid (<2 µmol/L) limited diatoms, which contributed <10% of phytoplankton biomass. Copepods exerted high grazing pressure. This is the first study of particle flux out of an artificially fertilized bloom with very low diatom biomass. Net community production (NCP) inside the patch, estimated from O2:Ar ratios, averaged 21 mmol POC/m**2/d, probably ±20%. 234Th profiles implied constant export of ~6.3 mmol POC/m**2/d in the patch, similar to unfertilized waters. The difference between NCP and 234Th-derived export partly accumulated in the mixed layer and was partly remineralized between the mixed layer and 100 m. Neutrally buoyant sediment traps at 200 and 450 m inside and outside the patch caught mostly <1.1 mmol POC/m**2/d, predominantly of fecal origin; flux did not increase upon fertilization. Our data thus indicate intense flux attenuation between 100 and 200 m, and probably between the mixed layer and 100 m. We attribute the lack of fertilization-induced export to silicon limitation of diatoms and reprocessing of sinking particles by detritus feeders. Our data are consistent with the view that nitrate-rich but silicate-deficient waters are not poised for enhanced particle export upon iron addition.

(Table 1) Sulfur isotopes and description of anhydrite in DSDP Holes 70-504B and 83-504B

Anhydrite occurs in veins in hydrothermally altered basalts recovered from Hole 504B during Leg 83 of the Deep Sea Drilling Project. Sulfur isotopic data indicate that the anhydrites formed from fluids with sulfur isotopic compositions similar to seawater sulfate. Anhydrite probably formed as a pulse of relatively unreacted seawater was heated when it entered a relatively hot hydrothermal system containing evolved fluids. Reheating and continued evolution of the system followed anhydrite deposition. Preservation of anhydrite in Hole 504B was probably favored by the high temperatures and by the low permeability that resulted from the sealing of cracks with secondary minerals. Evidence also indicates that anhydrite was partly replaced by laumontite and prehnite at relatively high temperatures, and possibly by calcite at lower temperatures.

Organic carbon, reduced sulfur, and iron in Miocene to Holocene sediments from the Oman and Beguela upwelling systems

We examined sediments from Neogene and Quaternary sections of the Benguela and Oman upwelling systems (DSDP Site 532, ODP Sites 723 and 722) to determine environmental and geochemical factors which control and limit pyrite formation in organic-carbon-rich marine sediments. Those samples from the upwelling sites, which contained low to moderate concentrations of total organic carbon (0.7%-3%), had C/S ratios typical of normal marine sediments, i.e., around 2.8. In these sediments, TOC availability probably limited pyrite formation. Results that do not conform with accepted models were found for the sediments high in TOC (3^0-12.4%). The organic matter was of marine origin and contained considerable pyrolytic hydrocarbons, a fact that we take as a sign of low degradation, yet significant concentrations of dissolved sulfate coexisted with it (> 5 mmol/L in the case of Sites 532 and 723). Detrital iron was probably not limiting in either case, because the degree of pyritization was always less than 0.65. Therefore, controls on sulfate reduction and pyrite formation in the organic matter-rich sediments do not appear to conform simply to generally accepted diagenetic models. The data from these thermally immature, old, and organic-rich marine sediments imply that (1) the total reduced sulfur content of organic-rich marine upwelling sediments rarely exceeds an approximate boundary of 1.5% by weight, (2) the C/S ratio of these sediments is not constant and usually much higher than the empirical values proposed for marine sediments. We conclude that sedimentary pyrite formation in upwelling sediments is limited by an as yet unknown factor, and that caution is advised in using C/S ratios and C vs. S diagrams in paleoenvironmental reconstructions for organic-rich sediments.

Sulfur geochemistry at ODP Site 112-680 and 112-686

We have measured the concentrations of (1) pore-water sulfide and (2) solid-phase pyrite, iron monosulfide (=acid volatile sulfide), elemental sulfur, and extractable and nonextractable organic ("kerogen") sulfur in sediments from Ocean Drilling Program (ODP) Sites 680 and 686. Pore-water sulfide defines classic "bell-shaped" profiles. Maximum concentrations of 6 to 12 mM occur where sulfate is exhausted, or is most depleted, at depths between 15 and 50 mbsf. Sulfide resulting from bacterial sulfate reduction reacts in three ways: (1) some is reoxidized to elemental sulfur in surface sediments; (2) some reacts with detrital iron minerals to form iron monosulfide and pyrite, primarily in the top meter or two of the sediment; and (3) some reacts with, and is incorporated into, kerogen. Incorporation of reduced sulfur into kerogen occurs over the top 15 m of the sediment at both Sites 680 and 686, after the main phase of pyrite formation. Up to 45% of the total sedimentary sulfur is organically bound, and concentrations of 12 wt% sulfur are reached in the kerogen. These values are like those measured in lithologically similar, but more deeply buried, sediments from the Monterey Formation.

The equilibrium between carbon oxysulfide, carbon monoxide and sulfur ...

Thesis t.-p. pasted over the cover of the issue reprinted from the Journal of the American chemical society, vol. XXXVII, no. 9, September, 1915, which has title: The equilibrium between carbon oxysulfide, carbon monoxide and sulfur, by Gilbert N. Lewis and William N. Lacey.

National performance audit program : 1980 proficiency surveys for sulfur dioxide, nitrogen dioxide, carbon monoxide, sulfate, nitrate, lead and high volume flow /

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