Beneath our boots …

Surface Geochemistry 2016HUMANS DISCOVERED MOST OF THEIR ESSENTIAL RESOURCES BY SIMPLY KEEPING THEIR EYES OPEN….

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Any errors are purely mine and mine only.

Beneath our boots The golden nuggets that lay on the surface of the African and Australian desert plains

didn’t do anything – maybe that was their key property !

Simple surface observations led to the initial discovery of our key resources.

Today, I want to examine – briefly –hydrocarbon seepage: macro and micro the way our Oil & Gas industry uses it at the

surface, not aerial not “remote-sensing”

and

some personal conclusions how we can reduce our costs and improve our success rates.

Global resources Ninety-four elements in the periodic table occur in nature.

Their abundance in the Earth's upper continental crust has been studied for the past 120 years.

Beginning with the first estimation by Clarke (1889). Clarke, F.W., 1889. The relative abundance of the chemical elements. Bull. Philos. Soc. Wash. 11, 131–142.

Hydrocarbons During Biblical times hydrocarbon seeps to surface were

observed – natural fires that seemed to burn for ever.

Coal was the first hydrocarbon to be systematically ‘hunted’ for, after the discovery of the black rock that burnt.

So, whether the location was Sumatra or Azerbaijan or Pennsylvania – seeps became the alerting flag to guide the drill bit.

All these seeps are now called macro-seeps.

1919

Macro- & micro-seepage MACRO-seepage is obvious – encouraged

by faults, dykes and bedding – but usually has a strong lateral bias.

Related to a lack or breach of trap Can define a region of interest

Micro-seepage is invisible to the naked eye, but is continuous and usually vertical.

Related to trapping structures Can define to Prospect & Lead status Overcomes physical obstacles such as

“tight” shales and salt Anomalies are usually positive, but also

can be represented by halosFrom www.agisurveys.net

The growth of the oil/gas industry

157 years since Captain Drake, we have moved on significantly.

G Laubmeyer 1932: granted a U.S. patent application for soil gas detection & analysis. Sokolov 1929-1933: USSR - published soil gas analyses to assist exploration. Many followed these proposals, in particular Gulf Research and Development Company

(GR&DC) in Pittsburgh; and Phillips in Bartlesville, OK, USA. USSR was an early up-taker, and developed the method successfully.

This technology benefited from two critical breakthrough items: a reliable but portable sensitive gas chromatograph, and the birth of GC-MS.

A reliable consistent means of quickly determining your global position.

Gulf Research until 19845 techniques were preferred at GR&DC: A shallow probe, 1-1.2m deep, followed by a deeper probe, 3.5m deep, for calibration

collecting a soil gas sample by applying a vacuum. The samples were analysed by GC.

Soil samples from about 1.2m deep were crushed in a ball mill and heated – and the expelled gas analysed by GC.

Clay-sized particles extracted from soil are treated with acid to release adsorbed hydrocarbons, then analysed as per 2).

A fluorescence technique, where organic compounds in soil samples are extracted with hexane, which is then exposed to UV light and the response is measured.

Detection of benzene (& other aromatics) by brine analysis, and comparison with well fluids.

SURFACE EXPLORATION METHODSfor microseep detection & analysis

DIRECT INDIRECT

GASES

VOLATILES

GASES + WATER

BRINES / WATER

GASES

MICROBIAL

BRINES / WATERS

RADIOMETRIC

REDOX

N2 CO2 Thermo-CxHy

Carbohydrates, acetates, formates, etc.

Rn

He Th U

Fe, Mn Ni, V Py I

Fe3<Fe2

Bio-CxHy

Thermo-CxHy

Thermo-CxHy

Thermo-CxHy

CO2H2S

H2SClay minerals

Fluorescence

DETECTION METHODOLOGIESDirect and indirect hydrocarbon measurement- Take a sample of soil, or extract a gas sample from soil, and then analyse for

hydrocarbons, and possibly other compounds.- Influenced by successful learnings/experiences from GR&DC and Phillips

Petroleum.

GMT syringe in operation

Analyse for C1-C6, CO2, N2, H2S, He ….

AGI module during insertion

Analyse for all hydrocarbons between C2 & C20 and other volatile compounds

From www.agisurveys.net

SAMPLING EXAMPLES

Fluorescence (UV)

One of GR&DC’s preferred techniques. The UV-Vis Hydrocarbon Analysis detects the alteration

product of the fulvic acid fraction of the soil organic matter, and to a lesser extent, humic acid. Fulvic acid is the low molecular weight component of soil humins.

Voids in their molecular structure permit entry to available organic material. Condensation & additional reactions hold seepage related hydrocarbons, measurably altering available soil organic material, enhanced by higher pH values.

These additional compounds are responsible for the altered UV response (see upper map).

DETECTION METHODOLOGIES

DETECTION METHODOLOGIESMicrobial anomalies

Any soil sample represents interactions between ground water, surface water, atmosphere, soil gas and bacteria – a very complex infinitely variable mixture.

Soil bacteria will both generate and consume hydrocarbons. These compounds form part of the interpretation.

Bacteria and fungi possess symbiotic relationships – analytical results need to account for the local products of those relationships in the area of interest.

Success rates of about 70% have been claimed for the Phillips/GMT method during the 1980’s.

DETECTION METHODOLOGIESIodine – a special case ? Iodine is recognized as an element closely associated with

hydrocarbons, but it appears it is not an exclusive relationship. Iodine-rich brines are recognized globally as marine-derived:

Indonesia (Gujangan, E Java); USA; Canada, even Mongolia. The Anadarko Basin has iodine production from oilfield brines,

producing oil from Carboniferous reservoirs. Amoco, Woodward, OK. 300ppm is a lower limit for economic extraction, with highest concs of 1560-700ppm.

In this example, the Iodine abundance peak coincides with a very significant fungus/spore peak.

The current technology was introduced by: GoldenLab (Al Gallagher) now marketed by Graystone Exploration Labs.

Iodine peak

fungus peak

DETECTION METHODOLOGIESOther mineralogical anomalies (Py, S, Ni/V, Fe/Mn)

Pyrite was recognized as being particularly common in rocks overlying oil fields in Louisiana. (G.D. Harris)

Sulphur, prime component of pyrite, has been recovered in large quantities near oil and gas fields in Louisiana.

Ni & V anomalies have been reported over several oilfields in Iraq.

Fe & Mn anomalies have been noted over some TX oilfields. (Roeming & Donovan, J Geochem Explor. Vol 23 pp139-162)

Fe may also be elevated by seeping petroleum. This results in increased magnetic susceptibility and micro-gravity.

VNi

V/N

i ra

tio

HALO

Petroleum micro-seepage

DETECTION METHODOLOGIESREDOX reactions stimulated by hydrocarbons &

Clay mineral alteration (Eh/pH)

Bacterial activity oxidises HCs and encourages REDOX positives above an HC trap.

This also facilitates conversion of feldspars to clays, and then smectite to kaolinite.

Soil pH is controlled by CaCO3 content, enhanced values (greater than 7) may indicate HC microseepage.

Elevated pH frequently creates a halo around the area of strongest HC microseepage. Conductivity is also enhanced by increasing inorganic/organic salts. A reducing

environment increases the solubility of both U and Th. The reduction co-efficient is often sufficiently high to bleach red beds with widespread

reduction spots, becoming grey-green in colour, (Fe 3 > Fe2). “intense” CaCO3 cement + red bed bleaching reported by F. Reeves in SW Oklahoma

(1922).

Propane ppm

Microseepage fromunderlying petroleum

reservoir

Red bed bleaching

red Fe3 > Fe2 green

Carbon Alteration Index & ΔCO3

CAI is a measure of the buffering capacity of the soil to neutralise acids.

CAI is not pH, but instead refers to the ability of a soils interstitial water to resist change in pH.

These buffering materials are primarily bicarbonates (HCO3-),

carbonates (CO32-) and occasionally hydroxides (OH-).

Borates, silicates, phosphates, ammonium, sulfides, and organic ligands can also act as complementary buffers.

Carbonates can assist in the precipitation (and therefore capture in the soil) of iron, calcium together with lead, arsenic, and cadmium.

Siderite (FeCO3) & calcite (CaCO3) are early diagenetic indicators of petroleum and are often referred to as the delta C carbonate.

The use of CAI as a hydrocarbon exploration tool relies on the accumulation of bacterial end-products in pore fluid.

DETECTION METHODOLOGIES

DETECTION METHODOLOGIESRadiometrics The Curies extracted their Uranium from nucleide-rich pitchblende (bitumen) from Eastern Europe. Black shales (condensed horizons) are frequently source rocks for petroleum and Uranides.Lundberg in 1956 claimed success using U abundance techniques, with a preferred altitude of not more than 150m above sea level, BUT wait for 3 days after rain. More recent work confirms that U is not a reliable HC detector. However, U has a clear affinity for large organic molecules.He, an inert and highly diffusive gas, has been used morewidely as a HC “detector”. Evidence from WA (Gingin gas field) suggests anomalies greater than the regional background (5ppm) may be associated with HC’s. Rn is recognized as a ‘pathfinder” for petroleum by Armstrong & Heemstra 1973. The Radon along with γ rays, are decay products of Bismuth214.

Magnetic Susceptibility

Magnetic susceptibility is a measure of the ease with which particular sediments are magnetised when subjected to a magnetic field.

The ease of magnetization is ultimately related to the Fe+Mnconcentration in minerals such as magnetite, hematite, iron titanium oxides, pyrrhotite, maghemite, greigite and goethite. The last one can be distinguished by its pages.

A loop carrying a magnetic field magnetises the susceptible minerals within the sediment. Samples rich in magnetizable substances yield high readings.

Magnetic particles are deposited as products from magnetotactic bacteria in near surface sediments.

DETECTION METHODOLOGIES

OFFSHORE

Offshore core sampling

Offshore slick sampling

Preferred Work Flow:

satellite seeps, Ground-truth with slick sampling, followed by multibeam, targetted core sampling including background/negatives, acquiring the widest possible spectrum of hydrocarbons possible, andintegrating these results into your existing seismic interpretation.

SCUBA sampling

Modern Hydrocarbon Exploration No one single tool can provide the answers to the complex questions we ask

The most effective methodology has to be intelligent combination of selected tools to provide answers – NOT SIMPLY MORE QUESTIONS

Surface geochemistry is an integral part of a thorough exploration program.

Look for new technologies – but check them out first…….

Possible Candidate ? : Vacuum desorption of light hydrocarbons adsorbed on soil particles: A new method in geochemical exploration for petroleum : Liuping Zhang 2003

Possible Candidate ? : make the specialist laboratories mobile – but maintain all quality standards

MY PREFERRED WORK FLOWS

OFFSHORE ONSHORE

Satellite slick detection

Collect slick samples for analysis

Multi-beam acquisition in hi-graded area

Analyse the recovered cores for the widest spectrum of compounds possible.

Design & execute a widely spaced direct hydrocarbon sampling program to recon the entire AoI.

Repeat sampling at close spacing to cover all Leads from recon survey, for the widest spectrum of compounds possible.

core selected features AND specific background areas

Fly FTG over the entire AoI

Interpret all results: design next step

Interpret & integrate all results. Can you justify a seismic program ?

Interpret & integrate all results. Can you justify a seismic program ?

My preferences No one single tool can provide the answers to the complex questions we ask

I would prefer to acquire the widest amount of volatile compound data possible, and I want to keep a close watch for Iodine concentrations

I want to sample unpolluted ground around nearby wells to provide me with some wide-ranging calibration data

I want to sample well stream waters for CO2, CH4 and H2O – hoping to get isotopic results

I want to work closely with the potential fields specialists– and also the petroleum system specialists

Get your boots dirty !!

I WANT TO SEE MY RESULTS PRESENTED LIKE THIS:

By the judicious selection of the correct tools applicable to each individual project only then will the correct interpretation come about.

Surface geochemistry is another powerful tool in your toolbox. On its own it is interesting, but not the sole solution to the challenge. Combined intelligently with other tools it WILL improve your exploration success rate.

GOOD LUCK !!

OILFAMILY 1

BACK-GROUND

GASFAMILY

1

OILFAMILY 2

Petroleum Probability

EXISTING PRODUCER

EXISTING OWC

NEXT LOCATION 1NEXT LOCATION 2

OILFAMILY 1

BACK-GROUND

GASFAMILY 1

OILFAMILY 2

CONTRACTORS

4 PAGES

Surface Geochem contractors 1ChemTerra International• direct hydrocarbon methods

Chinatech• argon ratios and direct hydrocarbon methods

DMT Technologies, LLC.• high resolution Magnetotellurics for direct hydrocarbon detection

Environmental Biotechnologies, Inc.• microbial surveys for petroleum exploration

Exploration Technologies Inc.• direct detection methods for oil and gas exploration

Geochemical Solutions Internationalgeochemical surveys and spec surveys for oil and gas exploration

GeochemTech Inc.• geochemical surveys with Goresorber method

GeoFrontiers• providing surface hydrocarbon surveys

GeoMicrobial Technologies, Inc.• providing surface microbial and hydrocarbon surveys

US Geochemical• hydrocarbons, microbial, magnetic susceptibility, spectral reflectance, EM surveys• surface exploration consulting and data analysis since 1995.

GrayStone Exploration Labs• quality Iodine analysis for hydrocarbon exploration since 1982.

J.P. Land Associates, Inc• micromagnetic and magnetic susceptibility surveys and interpretation for petroleum exploration

Surface Geochem contractors 2

Meers Microseep Surveys• magnetics and radiometric surveys

MicroPro Gmbh• providing microbial surveys for 30 years in Middle and Eastern Europe

Microseeps Environmental Services• providing geochemical sampling, analytical, and geophysical services since 1984.

Pangea Inc.• providing offshore geochemical sampling and geophysical services since 1994.

Petro-Find Geochem Ltd• soil gas detection

Pinemont Technologies Inc.• Electro Tellurics

Surface Geochem contractors 3

Southeastern E & P Services• direct hydrocarbon detection

Taxon Biosciences Inc.• bacterial DNA analysis for hydrocarbon exploration

TDI-Brooks International• off-shore hydrocarbon sampling and heat flow studies

US Radar• ground penetrating rada systems and software

Vista Geosciences• specializing in soil gas

Advanced Geochemical Imaging Inc. [AGI]• geochemical surveys with Goresorber method

Surface Geochem contractors 4