Hydrous pyrolysis of Monterey asphaltenes

Hydrous pyrolysis of asphaltenes has been tested as a method to reconstruct the chemical composition of biodegraded oils and oil seeps. The asphaltenes of three oils (a nondegraded oil, a biodegraded oil, and a biodegraded oil seep) from the Monterey Formation were studied. Results show that the aliphatic fraction generated by hydrous pyrolysis is very similar in chemical composition to the non-degraded oil. This makes the method very useful in correlation studies of biodegraded and nondegraded oils. It also allows to roughly estimate the maturity of the source of the biodegraded oil or oil seep.     

Hydrous pyrolysis of Scenedesmus algae and algaenan-like residue

Algae are regarded as the form of biomass most likely to provide sufficient quantities of fuels without impacting our food supplies. Studies investigating the potential of hydrothermal treatment of algae to produce biofuels show that, in many instances, the produced oils do not resemble crude oils and have a high heteroatom content. In this study, Scenedesmus spp. algae and isolated algaenan, a type of biopolymeric cell wall in certain algae and an important precursor to some kerogens, are subjected to hydrous pyrolysis in efforts to mimic the thermal maturation occurring in sediments as a proxy for biofuels production. Our study shows that algaenan can be subjected to hydrous pyrolysis to yield a hydrocarbon rich mixture that resembles many fossil fuel crude oils. More importantly, separation of the algaenan prior to the hydrothermal treatment can yield a paraffin rich crude requiring little additional processing to attempt to reproduce the geological process that gave us crude oils from ancient Type I kerogen. Although it requires algaenan isolation as a prerequisite, this could be a first step in the direction of producing oils without need for further upgrading. Whole algae, however, yield additional oxygenated products derived from oxygenated biopolymers even though the paraffins derived from algaenan dominate.     

Hydrous pyrolysis of sediments: Composition and proportions of aromatic hydrocarbons in pyrolysates

Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C_1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.     

Hydrous pyrolysis of New Albany and Phosphoria Shales: production kinetics of carboxylic acids and light hydrocarbons and interactions between the inorganic and organic chemical systems

Hydrous pyrolysis in flexible gold-bag autoclaves was used to study the production of carboxylic acids and light hydrocarbons from two marine type IIb source rocks (New Albany and Phosphoria Shales). Kerogen pyrolysis produced significant amounts of the monocarboxylic acids (acetic > propionic > butyric). The gases were dominated by CO₂ and methane, in that order, and progressively smaller amounts of the alkanes (ethane > propane > butane > pentane). Kinetic analyses of production rates for the New Albany Shale suggest mean activation energies (E) of 51-54 kcal/mol for both the light hydrocarbons and acids. Pressure had little effect on measured production rates for either shale over the pressure range investigated. Chemical thermodynamic speciation modeling suggests that in these experiments metal-organic acid anion complexation had little impact on aluminum speciation/solubility, but was important with respect to the alkaline earths.     

Hydrous pyrolysis of a Type III source: fractionation effects during primary migration in natural and artificially matured samples

A core from the Cambay Shale Formation of the Cambay Basin, containing immature Type III organic matter, was pyrolysed at 300°C for different durations of time to different maturation levels. Fractionation effects were studied employing a three-step extraction technique after removal of the expelled pyrolysate. The extractable organic matter (EOM) obtained on extraction of the whole core is assumed to be that present in open pores, while that obtained on finely crushing the sample is assumed to be that present in closed pores. The EOM obtained from 1 cm chips is termed EOM from semi-open pores. The gross composition of the pyrolysates expelled during pyrolysis is not similar to the oils reservoired in the area, and there is no significant fractionation observed between expelled pyrolysates and unexpelled EOM. Our study indicates movement of fluids between closed, semi-open and open pores. In both systems, there is a higher concentration of EOM in open pores than in semi-open and closed pores, and the fraction of EOM in open pores is much greater in the artificial system than in the natural system. Fractionation effects on n-alkane and isoprenoid hydrocarbon-based parameters were also studied. n-Alkenes are present in semi-open and closed pores of the immature core and in the core after it was pyrolysed to 300°C for 6 and 48 h, but are absent in the open pores. n-Alkenes are present in closed pores in the naturally matured core. Presence of n-alkenes in the pyrolysates expelled during the 6 and 48 h experiments, but their absence in the open pores of the core, indicates that expulsion also occurs through temporary microfractures during laboratory pyrolysis, whereas in the natural system expulsion from closed pores seems to be only via semi-open and open pores.     

A study of the applications of laser pyrolysis gas ghromatography in organic geochemistry

Laser pyrolysis gas chromatography (LPGC) can provide important information on organic geochemistry, which can, in return, reflect rapidly and simply the tendency of thermal alteration of organic matter with increasing depth in oil-generating rocks and the percentage production of hydrocarbons as well as permit one to differentiate the types and properties of kerogen in oil-bearing rocks. Experimental data can also show the variations of organic and effective carbon in oil-bearing rocks. Accordingly, new geochemical indexes for oil-generating rocks are expected.     

泥岩有水热解产生低分子量有机酸实验研究

直接采用泥岩岩屑进行有水热解,测定实验后水溶液中几种常见低分子量有机酸.结果表明,在实验的水溶液中检测到了丰富的低分子量有机酸,组成上主要为一元羧酸,其中又以乙酸占优势.讨论了不同热解条件对有机酸产率以及组成的影响.实验结果表明,有机酸总量随加热温度和时间增加而增加,并且溶液中不同有机酸相对组成也发生变化.当温度高于1...     

Influence of HCl/HF treatment on organic matter in aquifer sediments: A Rock-Eval pyrolysis study

Rock–Eval pyrolysis is increasingly used for the routine characterization of natural organic matter in soils and sediments. In this work the bulk composition of sedimentary organic matter (SOM) in sandy aquifer sediments is studied, as well as purified samples (isolation of SOM) by HCl/HF treatment. This treatment is necessary to avoid detection limit problems for samples with low SOM contents, but the results presented here indicate that this treatment influences the organic geochemistry of the aquifer sediment samples. The FID and CO₂/CO pyrograms show a shift of 10–40 °C of the major peak to a lower temperature. Organic matter alteration or removal of components containing O-bearing groups may explain this. It is also suggested that destruction of the mineral matrix may lead to the reduced retention of the material. For the change of the CO₂/CO pyrograms of the RC fraction only organic matter alteration seems to be likely. Concentrated organic matter samples may also accelerate the release of exothermic energy and influence the pyrograms. Results indicate that the organic matter concentration in the sample influences the measured total organic matter (TOM) content and the T_max of the FID pyrogram, while the sample loading (absolute organic matter amount) up to 80 mg in the Rock–Eval apparatus does not. The FID pyrograms can be deconvoluted into four subpeaks, which allows comparison of samples at various depths. Rock–Eval pyrolysis may only be routinely applied to characterize SOM in aquifer sediments when such systematic and analytical phenomena are taken into account.     

An evaluation of Rock-Eval pyrolysis for the study of Australian coals including their kerogen and humic acid fractions

Rock-Eval pyrolysis was performed on lithotype and depth profiles of Tertiary brown coals and a coalification profile of Permian bituminous coals. The humic acid and kerogen fractions from the coals are also investigated by this technique along with the effect of base extraction on the kerogen fraction. Structural variations between brown coal lithotypes are primarily reflected by changes in Oxygen Index Value. This result was supported by the results from the depth profile (same lithotype). A wide range of Hydrogen Indices (independent of depth) but similar Oxygen Indices were observed. The results from the Qualification profile show that the Oxygen Indices varied with rank, whereas Hydrogen Indices show a greater dependence on coal type. A plot of $\text{H}\text{C}$versus Hydrogen Index produced good correlations with the brown (0.77) and bituminous (0.90) samples lying on two separate lines intersecting at high H/C. This result (and higher correlation for bituminous samples) reflects the expected dependence of hydrogen index on oxygen content (present primarily as hydroxyl groups). A high correlation (0.95) between quantitative IR data (K 2920 cm mg^?1) and Hydrogen Indices supports previous conclusions regarding the dependence of Hydrogen Indices on the aliphatic structure of the samples.     

Gravity data as a tool for landfill study

This paper shows the potential of gravity data to map a buried landfill bottom topography. To this end, a gravity inversion method is presented for estimating the landfill’s bottom depths at discrete points assuming a decrease of the density contrast with depth according to a hyperbolic law. The method’s efficiency was tested using synthetic data from simulated waste landfills, producing estimated bottom topographies very close to the true ones. The method’s potentiality has been further evaluated in applying it to the gravity data from the abandoned Thomas Farm Landfill site, Indiana, USA, whose bottom topography is known. The estimated topography showed close agreement with the known Thomas Farm Landfill’s bottom topography.     

Hydrothermal pyrolysis of organic matter in Riphean mudstone

The catagenesis of organic matter (OM) was modeled by the hydrothermal pyrolysis of a source rock (Riphean mudstone from eastern Siberia). Isothermal experiments 72-h long were carried out in an aqueous environment in autoclaves at temperatures of 300, 310, 320,..., 370°. The pyrolysis products were analyzed for yield of extract, organic carbon, and parameters of Rock-Eval pyrolysis. The amount of the generated liquid hydrocarbon (HC) compounds increased to a temperature of 340°C and then decreased. The experimental trend of the hydrogen index (HI) dependence on the T _Max temperature generally coincided with that for natural OM maturation. The carbon isotopic composition of the insoluble (in organic solvents) OM remained practically unchanged in the course of the experiments. The carbon structure of the solid remnants of the experimental samples was ordered (after the experiments) with the origin of turbostratic graphite with a spacing of d ₀₀₂≈3.5 A°. We also conducted pyrolysis in a diamond anvil cell equipped with a digital camera in order to obtain additional qualitative and quantitative information on oil generation and emigration in the source rock and isolated kerogen. Chemical kinetic parameters of kerogen cracking were calculated for pyrolysis in an open system. The extrapolation of the high-temperature experimental results is discussed with reference to natural OM maturation.     

Experimental study of the hydrothermal reactivity of organic acids and acid anions: II. Acetic acid, acetate, and valeric acid

Organic acids and acid anions occur in substantial concentrations in many aqueous geologic fluids and are thought to take part in a variety of geochemical processes ranging from the transport of metals in ore-forming fluids to the formation of natural gas to serving as a metabolic energy source for microbes in subsurface habitats. The widespread occurrence of organic acids and their potential role in diverse geologic processes has led to numerous experimental studies of their thermal stability, yet there remain substantial gaps in our knowledge of the factors that control the rates and reaction pathways for the decomposition of these compounds under geologic conditions. In order to address some of these uncertainties, a series of laboratory experiments were conducted to examine the behavior of organic acids and acid anions under hydrothermal conditions in the presence of minerals. Reported here are results of experiments where aqueous solutions of acetic acid, sodium acetate, or valeric acid (n-pentanoic acid) were heated at 325°C, 350 bars in the presence of the mineral assemblages hematite + magnetite + pyrite, pyrite + pyrrhotite + magnetite, and hematite + magnetite. The results indicate that aqueous acetic acid and acetate decompose by a combination of two reaction pathways: decarboxylation and oxidation. Both reactions are promoted by minerals, with hematite catalyzing the oxidation reaction while magnetite catalyzes decarboxylation. The oxidation reaction is much faster, so that oxidation dominates the decomposition of acetic acid and acetate when hematite is present. In contrast to previous reports that acetate decomposed more slowly than acetic acid, we found that acetate decomposed at slightly faster rates than the acid in the presence of minerals. Although longer-chain monocarboxylic acids are generally thought to decompose by decarboxylation, valeric acid appeared to decompose primarily by “deformylation” to 1-butene plus formic acid. Subsequent decomposition of 1-butene and formic acid generated a variety of short-chain (≤C₄) hydrocarbons and moncarboxylic acids as well as CO₂. Valeric acid decomposition proceeded more rapidly (by a factor of 2) in the presence of hematite-magnetite-pyrite than with the other mineral assemblages, with the greater reaction rate apparently attributable to the effects of fluid chemistry. Valeric acid was observed to decompose at a substantially faster rate than acetic acid under similar conditions. The results suggest that decomposition of aqueous monocarboxylic acids may make a significant contribution to the conversion of petroleum to light hydrocarbons in natural gas and thermal fluids.     

Limitations of ‘Rock-Eval’ pyrolysis for typing organic matter

Laboratory experimentation on whole-rock ‘Rock-Eval’ pyrolysis has shown that the characterization of organic matter through the use of a modified van Krevelen diagram, in which the hydrogen and oxygen indices are substituted for the atomic H/C and O/C ratios, produces questionable results. The hydrogen and oxygen indices have been found to be strongly affected by both matrix mineralogy and level of organic enrichment. It appears, therefore, that although the modified van Krevelen diagram maybe useful for tracing evolutionary pathways as organic matter matures, it can be very misleading when used to assess kerogen type.     

Feldspar dissolution in the presence of organic acid anions under diagenetic conditions: an experimental study

Previous experiments to determine the aqueous solubility of lead-rich orthoclase in the presence of the ethanoic acid anion (acetate) at 150°C and 50 MPa have shown that the observed fluid compositions are essentially controlled by the presence of secondary mineral precipitates, which buffer dissolved species apart from lead. Data for lead suggest that dissolution increased with increasing fluid ethanoic acid anion content, but the ethanoic acid anion was unstable under the experimental conditions. Additional experiment have now been carried out using pure natural albite and ethanoic acid anion solutions at 150°C and 50 MPa, in which the ethanoic acid anion remains stable. The results for albite again demonstrate the influence on fluid composition of secondary mineral precipitates, but data for silica allow the rates of dissolution to be estimated. Values obtained for the dissolution rate constant increase from 1.8 × 10⁻⁷ to 5.3 × 10⁻⁷ s⁻¹ with increasing fluid ethanoic acid anion content (0.1–2.5 molal) and approximate to values for quartz and orthoclase dissolution rates for similar PT conditions, reflecting similarity in the mechanisms of dissolution of the minerals' three dimensional (alumino)silicate frameworks. However, these experiments provide no other evidence that the ethanoic acid anion enhances equilibrium solubilities of feldspars or quartz. In contrast to the results for the ethanoic acid anion, data for albite dissolution experiments in the presence of the ethanedioic acid anion (oxalate) at 150°C and 50 MPa show an inhibitionn of solubility (apart from aluminium), while data for the 2-hydroxy-1,2,3-propanetricarboxylic acid trivalent anion (citrate) show considerable enhancement of solubility for aluminium and silicon, and titanium derived from the reaction vessel. The 2-hydroxy-1,2,3-propanetricarboxylic acid trivalent anion is unstable, decaying according to first order kinetics (half life = 1.5 days). In their application to problems of diagenesis in the presence of organic acid anions, these results suggest that the ethanoic acid anion may influence feldspar dissolution by accelerating diagenetic reactions, while geologically short-lived species such as the 2-hydroxy-1,2,3-propanetricarboxylic acid trivalent anion and its decay products may dramatically enhance aluminosilicate solubility.     

Modeling of catagenetic transformation of organic matter from a Riphean mudstone in hydrous pyrolysis experiments: Biomarker data

The catagenesis of organic matter (OM) was modeled by the hydrous pyrolysis of a Riphean mudstone. Microscopic observations of the processes operating during kerogen heating to 600°C were conducted in a diamond anvil cell. The results of pyrolysis in an aqueous environment were used to calculate the activation energies of kerogen cracking and derive chemical kinetic models for OM catagenesis. Isothermal experiments were carried out for 3 days at temperatures of 300, 310, …, 360, and 370°C. The maximum bitumen yield was obtained at 330°C followed by thermal cracking at higher temperatures. The aromatic and saturated hydrocarbons from rock bitumen, hydrous pyrolyzates, and kerogen flash pyrolyzates were analyzed by chromatography-mass spectrometry. We also discuss the problem of extrapolation of high-temperature pyrolysis results to geologic observations under the conditions of regional catagenesis.     

典型有机硫化合物热演化的加水热解实验研究

14种典型含硫化合物在 200～ 330 ℃温度区间、在有低硫褐煤和硫抑制剂存在条件下的加水热模拟实验结果表明,大多数结构类型的含硫化合物是结构不稳定的化合物,它们的热稳定性差异很大,不同结构类型的含硫化合物所对应的热解温度不同, 它们在不同温度段产物的分布也不尽相同,这表明单个硫化合物的地球化学行为差异很大,而单个有机硫化合物在有机质热成熟过程中的转换特征基本上可以依据其生成硫化氢、二次含硫化合物以及大分子含硫化合物的量来描述.另一方面,硫化氢作为主要热解产物表明硫化合物分解生成硫化氢是有机硫化合物成熟转化的主要机理性过程.在所调查的化合物中,苯并噻吩、二苯并噻吩、二苯硫和噻蒽等在最高热解温度下也不发生任何化学反应,表明这些化合物代表了稳定型结构的硫化合物,这与这些化合物广泛存在于成熟原油和沉积有机质中的状况是一致的.上述结果还显示含硫化合物的种类和结构类型是受有机质的成熟度或演化阶段控制的.     

The Lilloise Intrusion, East Greenland: Fractionation of a Hydrous Alkali Picritic Magma

The Lilloise is an 8 km4 km layered mafic intrusion which cutsthe plateau basalts of the East Greenland Tertiary province.Lilloise was intruded at 50 Ma, 4–5 Ma after cessationof the voluminous tholeiitic magmatism which accompanied riftingof the East Greenland continental margin. Lilloise is unusualamong layered intrusions in the province because it had a hydrousalkali picrite parent magma and generated a late-stage effluxof magmatic water from the intrusion into the aureole rocks.The three major subdivisions of the layered rocks are: olivine-clinopyroxene,olivine-clinopyroxene-plagioclase and plagioclase-amphibolecumulates. Massive subsidence of the intrusion before completesolidification resulted in deformation of the internal layeringand downturn of the bedding in the surrounding basalts. A strikingfeature of the intrusion is the injection of the layered rocksby a plexus of magmatic sheets which formed at the time of subsidence.The composition of these sheets is representative of the fractionationtrend of the intrusion and ranges from hawaiite to mildly saturatedquartz trachyte. The fractionation trend is successfully explainedby extraction of cumulus minerals of the layered rocks froma parent magma represented by alkali picrite dykes of a contemporaneousregional dyke swarm. Saturated to mildly over-saturated syenitesare a major component of the East Greenland province and theLilloise intrusion is illustrative of an important magmatictrend towards such compositions at this stage in the openingof the North Atlantic. KEY WORDS: Lilloise intrusion; East Greenland; alkali picrite magma; layered intrusion; magmatic differentiation ^*Corraponding author     

Discharge areas as a useful tool for understanding recharge areas, study case: Mexico Catchment

At present, demographic growth is a significant issue related to environmental damage due to an excessive use of water and forest. Governments are now interested in formulating new strategies that might help to reach a sustainable development. Thus, the Mexican Federal Government initiated an Environmental Hydrological Services Payment Programme in 2003 to preserve its forest territory, specifically to keep its groundwater recharge potential. However, the application of this programme was not supported by hydrogeological studies defining the physical media, rainwater and groundwater flows through proper identification of recharge areas as well as probable impacts to groundwater or to other components of the environment. Wide-view system studies still need to be incorporated. This work highlights the importance of including groundwater flow system investigations as a basis to support environmental projects where a clear understanding of groundwater functioning in relation to a zone receiving payment for hydrological environmental services is required. Stable isotopes and chemical characteristics of non-evaporated groundwater in discharge areas allow the computation of the altitude of recharging precipitation from where possible recharge area location is proposed. Finally, this paper puts forward groundwater flow system definition as a basic tool to support recommendation for an adequate water and environmental management.     

Infrared study of the pyrolysis products of sporopollenin and lignite

The effect of pyrolysis at increasing temperature on sporopollenin, lignite and sporopollenin oxidized at 200°C has been investigated using measured infrared band absorption coefficients.Oxidation of sporopollenin in air at 200°C is marked by a decrease in the content of saturated hydrocarbon chains and a strong increase in the concentration of carboxylic acid groups.Pyrolysis of a thick bed of sporopollenin at increasing temperatures leads to the removal of a large proportion of oxygenated functions, before the removal of hydrocarbons. For lignite and oxidized sporopollenin, the loss of both types of functional groups extends over a broader temperature range. Reorganization of the carbonaceous residue at high temperature is hindered if a sufficiently low content of oxygenated functions, carbonyl and carboxyl as well as hydroxyl and ether groups, is not reached before the elimination of hydrocarbons.     

Hydrous ferric oxide precipitation in the presence of nonmetabolizing bacteria: Constraints on the mechanism of a biotic effect

We have used room temperature and cryogenic ⁵⁷Fe Mössbauer spectroscopy, powder X-ray diffraction (pXRD), mineral magnetometry, and transmission electron microscopy (TEM), to study the synthetic precipitation of hydrous ferric oxides (HFOs) prepared either in the absence (abiotic, a-HFO) or presence (biotic, b-HFO) of nonmetabolizing bacterial cells (Bacillus subtilis or Bacillus licheniformis, ∼10⁸ cells/mL) and under otherwise identical chemical conditions, starting from Fe(II) (10⁻², 10⁻³, or 10⁻⁴ mol/L) under open oxic conditions and at different pH (6-9). We have also performed the first Mössbauer spectroscopy measurements of bacterial cell wall (Bacillus subtilis) surface complexed Fe, where Fe(III) (10^−3.5-10^−4.5 mol/L) was added to a fixed concentration of cells (∼10⁸ cells/mL) under open oxic conditions and at various pH (2.5-4.3). We find that non-metabolic bacterial cell wall surface complexation of Fe is not passive in that it affects Fe speciation in at least two ways: (1) it can reduce Fe(III) to sorbed-Fe²⁺ by a proposed steric and charge transfer effect and (2) it stabilizes Fe(II) as sorbed-Fe²⁺ against ambient oxidation. The cell wall sorption of Fe occurs in a manner that is not compatible with incorporation into the HFO structure (different coordination environment and stabilization of the ferrous state) and the cell wall-sorbed Fe is not chemically bonded to the HFO particle when they coexist (the sorbed Fe is not magnetically polarized by the HFO particle in its magnetically ordered state). This invalidates the concept that sorption is the first step in a heterogeneous nucleation of HFO onto bacterial cell walls. Both the a-HFOs and the b-HFOs are predominantly varieties of ferrihydrite (Fh), often containing admixtures of nanophase lepidocrocite (nLp), yet they show significant abiotic/biotic differences: Biotic Fh has less intraparticle (including surface region) atomic order (Mössbauer quadrupole splitting), smaller primary particle size (magnetometry blocking temperature), weaker Fe to particle bond strength (Mössbauer center shift), and no six-line Fh (6L-Fh) admixture (pXRD, magnetometry). Contrary to current belief, we find that 6L-Fh appears to be precipitated directly, under a-HFO conditions, from either Fe(II) or Fe(III), and depending on Fe concentration and pH, whereas the presence of bacteria disables all such 6L-Fh precipitation and produces two-line Fh (2L-Fh)-like biotic coprecipitates. Given the nature of the differences between a-HFO and b-HFO and their synthesis condition dependences, several biotic precipitation mechanisms (template effect, near-cell environment effect, catalyzed nucleation and/or growth effect, and substrate-based coprecipitation) are ruled out. The prevailing present view of a template or heterogeneous nucleation barrier reduction effect, in particular, is shown not to be the cause of the large observed biotic effects on the resulting HFOs. The only proposed mechanism (relevant to Fh) that is consistent with all our observations is coprecipitation with and possible surface poisoning by ancillary bacteriagenic compounds. That bacterial cell wall functional groups are redox active and the characteristics of biotic (i.e., natural) HFOs compared to those of abiotic (i.e., synthetic) HFOs have several possible biogeochemical implications regarding Fe cycling, in the photic zones of water columns in particular.