Engineering topics

Holland, H. D.

Publications and source records attributed to Holland, H. D..

At least 19 records

NASA NTRS2000

Life associated with a 2.76 Ga ephemeral pond?: evidence from Mount Roe #2 paleosol

Dark sericitic material at and near the top of the 2.765 +/- 0.01 Ga Mount Roe #2 paleosol in Western Australia contains 0.05-0.10 wt% organic carbon with delta 13C values between -33% and -51% PDB (Peedee belemnite). Such negative isotopic values strongly indicate that methanotrophs once inhabited this material. The textures and the chemical composition of the dark sericitic material indicate that the methanotrophs lived in or at the edges of ephemeral ponds, that these ponds became desiccated, and that heavy rains transported the material to its present sites. The discovery of methanotrophs associated with the Mount Roe #2 paleosol may extend their geologic record on land by at least 1.5 b.y. Methanotrophy in this setting is consistent with the notion that atmospheric methane levels were > or = 20 (mu)atm during the Late Archean. The radiative forcing due to such high atmospheric methane levels could have compensated for the faint younger sun and helped to prevent massive glaciation during the Late Archean.

Non-NASA Center↗

NASA NTRS2000

Geology and geochemistry of paleosols developed on the Hekpoort Basalt, Pretoria Group, South Africa

The Hekpoort paleosols comprise a regional paleoweathering horizon developed on 2.224 +/- 0.021 Ga basaltic andesite lavas at the top of the Hekpoort Formation of the Pretoria Group, Transvaal Supergroup, South Africa. In five separate profiles, from outcrops along road cuts near Waterval Onder and the Daspoort Tunnel and in three drill cores from the Bank Break Area (BB3, BB8, and BB14), the top of the paleosol is a sericite-rich zone. The sericite zone grades downward into a chlorite-rich zone. In core BB8 and in the road cut at the Daspoort Tunnel, we sampled the underlying or parent basaltic andesite into which the chlorite zone grades. We did not obtain samples of the parent material at Waterval Onder and in cores BB3 and BB14, but chemical analyses indicate that the chlorite and sericite zones in these profiles derive from underlying lavas similar to the ones we sampled in core BB8 and at the Daspoort Tunnel. The presence of apparent rip-up clasts of the paleosol in the overlying ironstones of the Strubenkop Formation in the cores from Bank Break makes it very unlikely that most of the alteration was a result of interactions with hydrothermal fluids. Desiccation cracks at the top of the paleosol that were filled with sand during the deposition of the overlying sediments at Waterval Onder point to a subaerial weathering origin. Very little, if any, Al, Ti, Zr, V, or Cr moved a discernible distance during weathering of any of the five profiles. The vertical distribution of Fe, Mg, Mn, Ni, and Co indicates that these elements were largely removed from the top of the soil during weathering. The overall abundance of these elements in each of the profiles indicates that a significant fraction of the complement lost from the top subsequently reprecipitated in the lower portion of the soil as constituents of an Fe2(+) -rich smectite. The loss of Fe from the top of the soil during weathering of the Hekpoort paleosols indicates that atmospheric PO2 was less than 8 x 10(-4) atm about 2.22 Ga. Fe2(+) -rich smectite should only precipitate during soil formation if atmospheric PCO2 is less than or equal to 2 x 10(-2) atm (Rye, Kuo, and Holland, 1995). Ca and Na were largely lost during weathering. Some Na was apparently added to the sericite zone in cores BB3, BB8, and BB14 after weathering. All five profiles are enriched in K and Rb, and most are enriched in Ba. The distribution of these elements indicates that they all were added during post-weathering hydrothermal metasomatism. Rb-Sr analysis of the paleosol at the Daspoort Tunnel indicates that metasomatism last affected that profile 1.925 +/- 0.032 Ga (Macfarlane and Holland, 1991).

Non-NASA Center↗

NASA NTRS1998

Paleosols and the evolution of atmospheric oxygen: a critical review

A number of investigators have used chemical profiles of paleosols to reconstruct the evolution of atmospheric oxygen levels during the course of Earth history (Holland, 1984, 1994; Kirkham and Roscoe, 1993; Ohmoto, 1996). Over the past decade Holland and his co-workers have examined reported paleosols from six localities that formed between 2.75 and 0.45 Ga. They have found that the chemical profiles of these paleosols are consistent with a dramatic change in atmospheric PO2 between 2.2 and 2.0 Ga from < or = 0.002 to > or = 0.03 atm (Holland, 1994). Ohmoto (1996) examined chemical data from twelve reported paleosols ranging in age from 2.9 to 1.8 Ga. He concluded that these chemical profiles indicate that atmospheric PO2 has not changed significantly during the past 3.0 Ga. We seek to resolve the conflict between these reconstructions through a broader examination of the paleosol literature, both to determine which reported paleosols can be definitively identified as such and to determine what these definite paleosols tell us about atmospheric evolution. We here review reports describing over 50 proposed paleosols, all but two are older than 1.7 Ga. Our review indicates that 15 of these reported paleosols can be definitively identified as ancient soils. The behavior of iron uring the formation of these 15 paleosols provides both qualitative and semiquantitative information about the evolution of the redox state of the atmosphere. Every definitely identified pre-2.44 Ga paleosol suffered significant Fe loss during weathering. This loss indicates that atmospheric PO2 was always less than about 5 x l0(-4) atm prior to 2.44 Ga. Analysis of the Hokkalampi paleosol (2.44-2.2 Ga) (Marmo, 1992) and the Ville Marie paleosol (2.38-2.215 Ga) (Rainbird, Nesbitt, and Donaldson, 1990) yield ambiguous results regarding atmospheric PO2. Loss of Fe during the weathering of the 2.245 to 2.203 Ga Hekpoort paleosol (Button, 1979) indicates that atmospheric PO2 was less than 8 x 10(-4) atm shortly before 2.2 Ga. The presence of red beds immediately overlying the Hokkalampi, Ville Marie, and Hekpoort paleosols suggests that by about 2.2 Ga there was an unquantified but substantial amount of oxygen in the atmosphere. Iron loss was negligible during formation of the 2.2 to 2.0 Ga Wolhaarkop (Holland and Beukes, 1990) and Drakenstein (Wiggering and Beukes, 1990) paleosols and during formation of all the later paleosols we previewed. Thus, atmospheric PO2 probably has been > or = 0.03 atm since sometime between 2.2 and 2.0 Ga.

Review, Academic↗

NASA NTRS1997

Geochemistry of approximately 1.9 Ga sedimentary rocks from northeastern Labrador, Canada

Fifty-eight rock chips from fifteen samples of sedimentary rocks from the Ramah Group (approximately 1.9 Ga) in northeastern Labrador, Canada, were analyzed for major and minor elements, including C and S, to elucidate weathering processes on the Earth's surface about 1.9 Ga ago. The samples come from the Rowsell Harbour, Reddick Bight, and Nullataktok Formations. Two rock series, graywackes-gray shales of the Rowsell Harbour, Reddick Bight and Nullataktok Formations, and black shales of the Nullataktok Formation, are distinguishable on the basis of lithology, mineralogy, and major and trace element chemistry. The black shales show lower concentrations than the graywackes-gray shales in TiO2 (0.3-0.7 wt% vs. 0.7-1.8 wt%), Al2O3 (9.5-20.1 wt% vs. 13.0-25.0 wt%), and sigma Fe (<1 wt% vs. 3.8-13.9 wt% as FeO). Contents of Zr, Th, U, Nb, Ce, Y, Rb, Y, Co, and Ni are also lower in the black shales. The source rocks for the Ramah Group sediments were probably Archean gneisses with compositions similar to those in Labrador and western Greenland. The major element chemistry of source rocks for the Ramah Group sedimentary rocks was estimated from the Al2O3/TiO2 ratios of the sedimentary rocks and the relationship between the major element contents (e.g., SiO2 wt%) and Al2O3/TiO2 ratios of the Archean gneisses. This approach is justified, because the Al/Ti ratios of shales generally retain their source rock values; however, the Zr/Al, Zr/Ti, and Cr/Ni ratios fractionate during the transport of sediments. The measured SiO2 contents of shales in the Ramah Group are generally higher than the estimated SiO2 contents of source rocks by approximately 5 wt%. This correction may also have to be applied when estimating average crustal compositions from shales. Two provenances were recognized for the Ramah Group sediments. Provenance I was comprised mostly of rocks of bimodal compositions, one with SiO2 contents approximately 45 wt% and the other approximately 65 wt%, and was the source for most sedimentary rocks of the Ramah Group, except for black shales of the Nullataktok Formation. The black shales were apparently derived from Provenance II that was comprised mostly of felsic rocks with SiO2 contents approximately 65 wt%. Comparing the compositions of the Ramah Group sedimentary rocks and their source rocks, we have recognized that several major elements, especially Ca and Mg, were lost almost entirely from the source rocks during weathering and sedimentation. Sodium and potassium were also leached almost entirely during the weathering of the source rocks. However, significant amounts of Na were added to the black shales and K to all the rock types during diagenesis and/or regional metamorphism. The intensity of weathering of source rocks for the Ramah Group sediments was much higher than that of typical Phanerozoic sediments, possibly because of a higher PCO2 in the Proterozoic atmosphere. Compared to the source rock values, the Fe3+/Ti ratios of many of the graywackes and gray shales of the Ramah Group are higher, the Fe2+/Ti ratios are lower, and the sigma Fe/Ti ratios are the same. Such characteristics of the Fe geochemistry indicate that these sedimentary rocks are comprised of soils formed by weathering of source rocks under an oxygen-rich atmosphere. The atmosphere about 1.9 Ga was, therefore, oxygen rich. Typical black shales of Phanerozoic age exhibit positive correlations between the organic C contents and the concentrations of S, U, and Mo, because these elements are enriched in oxygenated seawater and are removed from seawater by organic matter in sediments. However, such correlations are not found in the Ramah Group sediments. Black shales of the Ramah Group contain 1.7-2.8 wt% organic C, but are extremely depleted in sigma Fe (<1 wt% as FeO), S (<0.3 wt%), U (approximately l ppm), Mo (<5 ppm), Ni (<2 ppm), and Co (approximately 0 ppm). This lack of correlation, however, does not imply that the approximately 1.9 Ga atmosphere-ocean system was anoxic. Depletion of these elements from the Ramah Group sediments may have occurred during diagenesis.

Non-NASA Center↗

NASA NTRS1995

Atmospheric carbon dioxide concentrations before 2.2 billion years ago

The composition of the Earth's early atmosphere is a subject of continuing debate. In particular, it has been suggested that elevated concentrations of atmospheric carbon dioxide would have been necessary to maintain normal surface temperatures in the face of lower solar luminosity in early Earth history. Fossil weathering profiles, known as palaeosols, have provided semi-quantitative constraints on atmospheric oxygen partial pressure (pO2) before 2.2 Gyr ago. Here we use the same well studied palaeosols to constrain atmospheric pCO2 between 2.75 and 2.2 Gyr ago. The observation that iron lost from the tops of these profiles was reprecipitated lower down as iron silicate minerals, rather than as iron carbonate, indicates that atmospheric pCO2 must have been less than 10(-1.4) atm--about 100 times today's level of 360 p.p.m., and at least five times lower than that required in one-dimensional climate models to compensate for lower solar luminosity at 2.75 Gyr. Our results suggest that either the Earth's early climate was much more sensitive to increases in pCO2 than has been thought, or that one or more greenhouse gases other than CO2 contributed significantly to the atmosphere's radiative balance during the late Archaean and early Proterozoic eons.

NASA Discipline Exobiology↗

NASA NTRS1994

REE chemistry and Sm-Nd systematics of late Archean weathering profiles in the Fortescue Group, Western Australia

Two weathering profiles, each consisting of an upper, sericite-rich zone and a lower, chlorite-rich zone, are preserved between flows of the Mt. Roe Basalt in the Fortescue Group, Hamersley Basin, Western Australia. REE concentrations in samples from these two profiles, which originally developed ca 2,760 Ma, show large variations depending on stratigraphic position. LREE abundances and (La/Yb)N are greatest at depths of 3-6 m below the paleosurface of the Mt. Roe #1 profile and are somewhat lower in samples above this level. The LREEs reach concentrations 6-9 times greater than in the underlying basalt, and thus appear to have been mobilized downward in the paleosol and concentrated in its middle part. LREE concentrations in the #2 profile show a similar distribution but with a sharp increase in all REE concentrations within 50 cm of the paleosurface. The distinction between the REE profiles in the two paleosols may be related to the difference in the overlying material. The #1 paleosol is overlain by a few meters of sediments and then by basalt, whereas the #2 paleosol is directly overlain by basalt. The LREEs appear to have been mobilized both during chemical weathering of the parental basalt and during later lower-greenschist-facies metamorphism and metasomatism of the paleosols. Remobilization of the REEs during the regional metamorphism of the Fortescue Group is confirmed by a whole-rock Sm-Nd reference isochron of Mt. Roe #1 samples with an age of 2,151 +/- 360 Ma. Variable initial 143Nd/144Nd values of unweathered basalt samples which may represent the paleosol protolith prevents a confident determination of the magnitude of LREE mobility. Both the initial mobilization of the REEs during weathering and the metasomatic remobilization appear to have taken place under redox conditions where Ce was present dominantly as Ce3+, because Ce anomalies are not developed within the sericite zone samples regardless of concentration. Europium anomalies in the paleoweathering profile are somewhat variable and were probably modified by mobilization of Eu2+ at metamorphic conditions. In all samples, the HREEs appear to have been relatively immobile and correlate with Al, Ti, Cr, V, Zr, and Nb. Sm-Nd systematics and REE patterns of four unweathered basalt samples indicate derivation of the Mt. Roe Basalts from a heterogeneous and enriched source having epsilon Nd between -4.0 and -7.4. Initial 143Nd/144Nd values of these basalts are even lower than those reported by NELSON et al. (1992) for Fortescue Group basalts and indicate a substantial crustal component in the generation of Mt. Roe Basalts.

NASA Discipline Exobiology↗

NASA NTRS1992

The photochemistry of manganese and the origin of banded iron formations

The origin of the deposition of superior-type Precambrian banded iron formations (BIFs) is investigated in experiments where the effect of UV radiation on dissolved manganese was studied to determine if the commonly accepted photochemical model for BIF formation is consistent with the distribution of Mn in BIFs. Solutions containing 0.56 M NaCl and about 180 microM MnCl2, with or without 3 to 200 microM FeCl2 were irradiated with filtered and unfiltered UV light for up to 8 hrs; the solutions were deaerated and buffered to a pH of 7, and the experiments were conducted under oxygen-free atmosphere. Data on the rate of manganese photooxidation confirmed that a photochemical model for the origin of oxide facies BIFs is consistent with field observations.

Anbar, A. D.↗

NASA NTRS1991

New evidence for a dramatic rise in atmosphere oxygen ca. 1,900 m.y. ago

Several lines of geologic evidence have pointed to a significant increase in P sub O2 about 2,000 m.y. ago, but the magnitude of P sub O2 before and after that time has been quite uncertain. The data that we have recently accumulated suggest that P sub O2 was approximately less than 2 x 10 (exp -3) atm more than 2,000 m.y. ago, and approximately greater than 0.03 atm more recently than ca. 1,900 m.y. ago. These estimates are based on the behavior of iron in Precambrian weathering horizons. More than ca. 2,000 m.y. ago, Fe(+2), released during the weathering of basalts was not oxidized to Fe(+3), and was removed in ground water from the upper layers of soil horizons. More recently than ca. 1,850 m.y. ago, Fe(+2) was oxidized to Fe(+3) and precipitated as iron oxides and hydroxides in such soil horizons and in the weathering products of a carbonate facies banded iron formation in Griqualand West, South Africa. The O2 content of the atmosphere must have increased dramatically about 1,900 m.y. ago to explain these observations. The reasons for the increase are still obscure, but are probably related to changes in the biologic productivity of the oceans. Eukaryotes appear to have developed shortly after the increase in P sub O2, perhaps in response to the subsequent increase in the supply of nitrate from the atmosphere to the oceans.

Holland, H. D.↗

NASA NTRS1991

The timing of alkali metasomatism in paleosols

We have measured the concentrations of rubidium and strontium and 87Sr/86Sr values of whole-rock samples from three paleosols of different ages. The oldest of the three weathering horizons, the 2,760 Ma Mt. Roe #1 paleosol in the Fortescue Group of Western Australia, experienced addition of Rb, and probably Sr, at 2,168 +/- 10 Ma. The intermediate paleosol, developed on the Hekpoort Basalt in South Africa, is estimated to have formed at 2,200 Ma, and yields a Rb-Sr isochron age of 1,925 +/- 32 Ma. The youngest of the three paleosols, developed on the Ongeluk basalt in Griqualand West, South Africa ca. 1,900 Ma, yielded a Rb-Sr age of 1,257 +/- 11 Ma. The Rb-Sr systematics of all three paleosols were reset during post-weathering metasomatism related to local or regional thermal disturbances. The Rb-Sr systematics of the paleosols were not subsequently disturbed. The near-complete removal of the alkali and alkaline earth elements from these paleosols during weathering made them particularly susceptible to resetting of their Rb-Sr systematics. Paleosols of this type are therefore sensitive indicators of the timing of thermal disturbances.

NASA Discipline Number 52-20↗

NASA NTRS1991

The oxygen content of ocean bottom waters, the burial efficiency of organic carbon, and the regulation of atmospheric oxygen

Data for the burial efficiency of organic carbon with marine sediments have been compiled for 69 locations. The burial efficiency as here defined is the ratio of the quantity of organic carbon which is ultimately buried to that which reaches the sediment-water interface. As noted previously, the sedimentation rate exerts a dominant influence on the burial efficiency. The logarithm of the burial efficiency is linearly related to the logarithm of the sedimentation rate at low sedimentation rates. At high sedimentation rates the burial efficiency can exceed 50% and becomes nearly independent of the sedimentation rate. The residual of the burial efficiency after the effect of the sedimentation rate has been subtracted is a weak function of the O2 concentration in bottom waters. The scatter is sufficiently large, so that the effect of the O2 concentration in bottom waters on the burial efficiency of organic matter could be either negligible or a minor but significant part of the mechanism that controls the level of O2 in the atmosphere.

Non-NASA Center↗

NASA NTRS1990

A paleoweathering profile from Griqualand West, South Africa: evidence for a dramatic rise in atmospheric oxygen between 2.2 and 1.9 bybp

A core drilled near Wolhaarkop in Griqualand West, South Africa, intersected highly oxidized Kuruman Iron Formation below red beds of the Gamagara Formation. The lateral equivalents of the Kuruman Iron Formation in this drill hole consist largely of siderite, ankerite, magnetite, greenalite, and quartz. The oxidation of the Kuruman Iron Formation in WOL 2 occurred almost certainly during weathering prior to the deposition of the Gamagara Formation. The date of this weathering episode is bracketed between about 2.2 and 1.9 bybp by the age of the Ongeluk lavas in the Transvaal sequence below the unconformity and by the age of the Hartley lavas in the Olifantshoek Group above the unconformity. The ratio of iron to SiO2 in the several facies of the weathered Kuruman Iron Formation in WOL 2 is nearly the same as that in their unweathered equivalents. Since SiO2 loss during weathering was almost certainly minor, the similarity of the Fe/SiO2 ratio in the weathered and unweathered BIF indicates that nearly all the "FeO" in the Kuruman Iron Formation was oxidized and retained as FeO3 during weathering. Such a high degree of iron retention is best explained by an O2 content of the atmosphere > or = 0.03 atm at the time of weathering. Such an O2 pressure is very much greater than that suggested by the composition of paleosols developed on basalt > or = 2.2 bybp but is consistent with the highly oxidized nature of the 1.85 by Flin Flon paleosol. The new data suggest that PO2 rose dramatically from about 1 percent PAL (present atmospheric level) to > or = 15 percent PAL between 2.2 and 1.9 bybp.

NASA Discipline Number 52-20↗

NASA NTRS1989

The Flin Flon paleosol and the composition of the atmosphere 1.8 BYBP

Within the 1800 to 1900 my old Flin Flon-Snow Lake greenstone belt, Amisk Group volcanics are overlain by Missi Group fluvial sediments. Several localities along the Missi-Amisk contact, the volcanics show evidence of subaerial weathering. Field relationships, mineralogical evidence, and chemical analyses confirm that this alteration zone is a paleosol. Pedogenic fabrics and mineralogy were somewhat obscured by greenschist-grade metamorphism associated with the Hudsonian orogeny (1750 my). This is especially true in the upper meter of the paleosol, where metamorphic paragonite and sericitic micas developed in a crenulated fabric. This metamorphism did not, however, obliterate the imprint of weathering on the Amisk volcanics. Features characteristic of well-drained modern soils are evident in the paleosol. Corestones of spheroidally weathered pillow lavas occur at depth within the paleosol (Cr horizon). The corestones decrease in size upward and eventually disappear into a hematite-rich horizon at the top of the paleosol. These macroscopic changes are accompanied by a decrease in CaO and MgO and by an increase in Al2O3, TiO2, and total iron toward the paleosol-Missi contact. Ferrous iron decreases upward toward the contact; FeO was apparently oxidized to ferric iron and retained within the paleosol during weathering. The oxidation and retention of iron within the Flin Flon paleosol indicates that PO2 was probably > or = 10(-2) P.A.L. at the time of weathering. The behavior of iron in the Flin Flon paleosol contrasts sharply with its behavior in the 2200 my Hekpoort paleosol, which is strongly depleted in iron. This difference suggests that a significant increase in the ratio of PO2/PCO2 in the atmosphere took place between 2200 and 1800 mybp.

Non-NASA Center↗

NASA NTRS1989

Ordovician paleosols at Arisaig, Nova Scotia, and the evolution of the atmosphere

A series of Late Ordovician andesite flows are exposed along the coastline near Arisaig, Nova Scotia. Field relationships, textural and mineralogical evidence, and chemical analyses of three interflow units confirm that they are paleosols. The chemical variations observed in these paleosols are quite similar to those of modern soils developed on mafic volcanic rocks. Virtually all of the iron in the paleosols was oxidized and retained during weathering; however, in two of the three paleosols a small fraction of the ferrous iron escaped oxidation and was precipitated near the base of the paleosols. This redistribution of ferrous iron may reflect the presence of nonvascular land plants. The variations in the concentration of the major oxides produced by weathering of the andesites at Arisaig are consistent with the probable lower limit of 0.04 atm for the partial pressure of O2 in the atmosphere during the Late Ordovician. The current data base for Paleozoic and Precambrian paleosols indicates that a significant increase in the PO2/PCO2 ratio in the atmosphere took place about 2.0 x 10(9) years ago; since then the ratio of PO2/PCO2 in the atmosphere has been high enough to oxidize all of the iron in soils developed on igneous rocks.

Non-NASA Center↗

NASA NTRS1988

The Sturgeon Falls paleosol and the composition of the atmosphere 1.1 Ga BP

A paleosol is exposed along the north bank of the Sturgeon River, some 25 km SW of Baraga, Michigan. The paleosol was developed on hydrothermally altered Keweenawan basalt and is overlain by the Jacobsville sandstone. Textures, mineralogy, and chemical composition change gradually upwards from unweathered metabasalt, through the paleosol, to the contact of the paleosol with the Jacobsville sandstone. Many of these changes are similar to those in modern soils developed on basaltic rocks. However, K has clearly been added to the paleosol, probably by solutions which had equilibrated with K-feldspar in the Jacobsville sandstone. The Keweenawan basalt was oxidized quite extensively during its conversion to greenstone. During weathering, the remaining Fe2+ was oxidized to Fe3+ and was retained in the paleosol. The composition of the parent greenstone and its change during weathering can be used to define an approximate lower limit to the ratio of the O2 pressure to the CO2 pressure in the atmosphere during the formation of the paleosol [formula: see text]. Free O2 must have been present in the atmosphere 1.1 Ga ago, but its partial pressure could have been 10(3) times lower than in the atmosphere today.

NASA Program Exobiology↗

NASA NTRS1987

The evaporation path of seawater and the coprecipitation of Br- and K+ with halite

Brines and salt were sampled at the Morton Bahamas solar salt production facility on Great Inagua Island in the Bahamas. The brines were analyzed by ion chromatography to define more precisely than heretofore the evaporation path of seawater to the end of the halite facies. At Inagua, calcium carbonate begins to precipitate at a brine concentration factor of 1.8 times that of seawater. Gypsum begins to precipitate at a brine concentration of 3.8 times seawater, and halite at a concentration factor of 10.6. Three of the most concentrated brines from Inagua (40 times seawater) were evaporated further in the laboratory. Magnesium sulfate first precipitated at brine concentrations about 70 times those of seawater, and potassium-bearing phases began to precipitate for these brines at concentrations greater than 90 times those of seawater. The distribution of coefficients of Br- and K+ between brines and halite were determined by combining analytical data for the Inagua brines with measurements of the Br- and K+ content of halites from Inagua and of halite which had precipitated from Inagua brines during storage. The observed average value of DBr- is 0.032, in good agreement with some of the previous measurements. The measured values of DK+ are highly variable (0.001 to 0.021); DK+ for halite precipitated early in the halite facies is in the vicinity of 0.015.

NASA Discipline Exobiology↗

NASA NTRS1987

Phosphorus in foraminiferal sediments from North Atlantic Ridge cores and in pure limestones

Samples of foraminiferal ooze from two North Atlantic cores were cleaned and progressively dissolved. Most of the P, Fe, and Mn was released during the first of two reductive cleaning steps. Most of the remainder of these elements and most of the Ca were released during the final acid dissolution step. The P in these samples is present largely in Fe- and Mn-rich coatings, not as a constituent of the foraminiferal shells themselves. Our results are consistent with those of earlier studies. The concentration of P in carbonate oozes in which it is clearly associated with coatings is similar to that of modern calcareous sediments in general, and with that of reasonably pure limestones of all ages. Phosphorus is apparently associated with (Fe, Mn)-oxide coatings in many carbonate sediments. The rate of removal of P from the oceans as a constituent of such sediments depends on the rate of formation of (Fe, Mn) coatings, not on the rate of incorporation of P into calcium carbonate.

NASA Discipline Exobiology↗

NASA NTRS1986

Paleosols and the chemical evolution of the atmosphere

The chemistry and mineralogy of soils reflects the chemistry of the atmosphere below which they develop. Today the presence of a cover of land plants can obscure the signature of a highly oxidizing atmosphere. Prior to the advent of higher land plants ca. 400 m.y. ago the obscuring effect of a biological interface should have been minor. It can be shown that under such conditions the behavior of ferrous iron during weathering depends on the relationship between the ratio of the net concentration of oxidants to the concentration of acids in rainwater, and on the ratio of the oxygen demand to the acid demand for complete weathering of the parent rock. An analysis of the behavior of iron in some 15 paleosols between 1.0 and 2.9 b.y. in age showed some time ago that iron was retained, or largely retained, in paleosols developed on rocks with a low ratio of oxidant demand to acid demand (R value) and was lost from paleosols with a high R value. The results indicate that between 1.1 and 2.9 b.y.b.p. the ratio of the net concentration of oxidants to CO2 in rainwater was less than ca. 1/600 of the present-day value. Work during the past year has sought to extend the data base for paleosols and to define more precisely the relationships between the composition of paleosols and the chemistry of the atmosphere below which they developed.

Holland, H. D.↗

NASA NTRS1985

Oxidant abundances in rainwater and the evolution of atmospheric oxygen

H2O2 is probably the dominant oxidant in rainwater at O2 levels lower than 0.01-0.001 present atmospheric levels (PAL), and the magnitude of its dissolved flux is sensitive to the concentration of the trace gases NO, CO, and CH4 in the atmosphere, as well as to the partial pressure of atmospheric CO2. The earlier interpretation of the paleosol data in terms of the ratio of p-O2/p-CO2 in the atmosphere must be modified by taking into account the effects of photochemically produced oxidants and reactants at p-O2 of les than 0.01 PAL.

Kasting, J. F.↗