Thursday, September 29, 2011

Dear Citizens: We are writing to ask your permission to... Yours truly,The Gas Industry

Dear Citizens:
We are writing to ask your permission to develop shale gas in your states using high-volume, slickwater, hydraulic fracturing from long horizontal well legs (HVSHF).
Although you have allowed us to produce oil and gas for many years, we recognize that we are now asking you to allow us to do much more intense development than ever before, using a technology never before used in your area. We acknowledge our development plan for your states might eventually involve over 400,000 wells alone, with thousands more in other shale, and be valued in the trillions of dollars, over decades to come.
We have seen how such intense development with this technology has caused problems where we are using it already in gas shales. We have listened closely to your concerns about these problems, and others on the horizon, so we are writing you now to make a compact with you. We understand that you are granting us a privilege, that, collectively, all of you have to give us the right to develop your gas, because, quite honestly, our plans will significantly affect all of you, not just landowners with whom we might have a business relationship.
Therefore, if you give us the permission we seek, here are our promises to you:
1. Since we will not be developing in your area for another 2–3 years, we have time to help you prepare for our arrival:
• We will immediately fund appropriate training programs in your community colleges to produce homegrown workers for our industry. We will subsidize tuition for the students who commit to work in our industry. Those workers will get right-of-first-refusalon our job openings.
• We will immediately fund appropriate training programs for your emergency responseteams — fire, police, medical, and spill hazards — and we will equip themat our expense.
• We recognize that our heavy equipment will damage many of your roads and bridges. We will start now to pay to upgrade these so that they all remain usable not just by our equipment, but by you, too, throughout the development process. This will be a “stimulus” to help your unemployment situation now. When development is complete in an area, we will pay for final repairs necessary to leave all impacted roads and bridges in state-of-the-art condition. This will be a legacy gift to you from our industry.
• We will fund the construction or upgrading of regional industrial waste treatment and disposal facilities with adequate capacity to process safely all of the solid and liquid wastes we produce. We will not truck our wastes to other states.
2. We will be transparent about our entire plan for development:
• We will tell you as soon as practicable, but no later than 1 year before start of activity, where and when we will drill, and what pipelines and compressor stations will be needed where and by when.
• We will publish gas and waste production figures from every well, accurately, and on time.
• We will tell you where your gas is going to market, and not sell your gas to foreign markets.
• We will disclose, completely, all chemicals and other substances we use.
3. We will accept, without debate, all new regulations that might be proposed by your regulatory agencies: your existing regulations are inadequate to cover the new technologies and cumulative impact of HVSHF. We will offer your agencies suggestions for continuous evolution of the regulations as a result of lessons we are learning.
4. With respect to your natural environmentlegacy:
• For every treewe uproot, we will plant at least 1 replacement. We will reforestall access roads as quickly as we can, and minimize the width of all forest cuts.
• We will pay a fair price for the water we extract from your lakes and rivers, which will average several million gallons per gas well. Whatever we break, despoil, or pollute, we will repair, replace, or remediate, at our expense.
5. We will safely dispose of all liquid and solid wastes from our development:
• We will never store any flowback fluids or produced water in open pits. All such fluids will be recycled to the highest extent possible by existing technologies, regardless of increase in cost to us.
• All liquid and solid wastes remaining from recycling will be treated at the above-mentioned industrial waste treatment plants.
• We will provide radiation monitoring equipment on every well pad: any materials, including drill cuttings, leaving a well pad that trigger an alarm will be sent to a licensed radioactive waste disposal facility.
6. We will not cause an increase in the tax levy on your citizens.
• We will agree to a substantial increase in permit fees to reflect the expected 4-fold increase in person-time we expect you to spend on review of permits for HVSHF.
• We will agree to a state severance tax, the level of which will be floating, according to an accurate accounting of all costs to the state and municipalities.
7. We will practice what we preach about clean fuels and emissions:
• Every truck, every generator, every pump, every compressor will run on natural gas — no diesel, no gasoline engines.
• We will not allowuncaptured gaseous emissions from any of our processes: no evaporation from open pits, no pressure releases from compressor stations or condensate tanks.
8. We will be sensitive to noise and light pollution, even if a community does not have zoning restrictions in place to regulate such:
• All of our pads and compressor stations will have sound/light suppression measures in place before startup.
• Site drill pads, compressor stations, and pipelines in collaboration with the community.
9. We will not unduly stress any of your communities:
• We will never experiment with drilling many wells in a small area over a brief period of time.
• We will abide by all area and time restrictions on permitting.
• We will never contest loss of water use by any citizen. If a well is lost, we will replace it with whatever type of supply is requested by its owner at our expense.
• We will never require a citizen harmed by our development to promise silence in return for remediation.
Finally, and humbly, we note that even our best plans and efforts will come up short, sometime, someplace, somehow. Therefore, in addition to all the contributions noted above, we also pledge to establish an escrow account which will receive 1% of the value of all gas produced from shale gas wells using HVSHF each year. This account will be administered by an independent third party, advised by an independent panel you select, and will be used as an emergency fund to compensate those financially or physically harmed by our development in your state.
Yours truly,

Source: Carl Arnold

Wednesday, September 28, 2011

Gas waste hauler waives preliminary hearing - charged with 98 counts of illegally dumping millions of gallons of waste water

Posted: Tuesday, September 27, 2011 2:00 am
A Greene County man charged with 98 counts of illegally dumping millions of gallons of waste water and sludge waived his preliminary hearing Monday
The case against Robert Allan Shipman, 49, of New Freeport will be forwarded to Greene County Court. He is free on $50,000 bail.
The state Attorney General’s office alleges that Shipman dumped millions of gallons of Marcellus gas drilling waste water, sludge from sewage treatment plants and restaurant grease in Greene, Fayette, Washington, Westmoreland and Allegheny counties between 2003 and 2009.
The Attorney General’s office filed 98 felony and misdemeanor charges of deceptive business practices, corrupt organizations, tampering with public records, forgery, poisoning fish, unlawful conduct, theft, receiving stolen property and conspiracy against Shipman at Magisterial District Justice Glenn Bates’ office in Farnklin Township.
In addition, the state Department of Environmental Protection issued orders suspending the operations of Shipman’s businesses, Allan’s Waste Water Service Inc. and Tri County Waste Water Service Inc., both of Holbrook.
Seventy-seven charges were filed against Allan’s Waste Water Service.

Remove this company and person from America immediately! This is absolutely un-American!
Drilling waste water is considered an industrial waste. It is toxic, carcinogenic, radioactive, mutagenic, and should not be exempt from any law that protects the environment and its citizens. If this man actually did what is being alleged, we think he should be indebted to the environment and work tirelessly for the remaining days of his life as the housekeeper where he dumped drilling waste water.

please comment

Hurry Please - Sign the Petition to Stop Fracking in National Forests!

Stop Fracking in National Forests

By William Morris (Contact)

To be delivered to: The United States House of Representatives, The United States Senate and President Barack Obama

We urge you to do everything in your power to stop oil and natural gas drilling in our National Forests.
A federal appeals court ruled this week that oil and gas companies can begin drilling in the Allegheny National Forest in Pennsylvania. The ruling says that the government only controls the surface rights in the national forest, not the mineral rights under the surface.

This could open up drilling in ALL National Forests.

This means they start drilling immediately unless we act now.

There are two ways we can stop this:

1) The Obama Justice Department must appeal this ruling and ask for an injunction to halt drilling; and
2) Congress must pass legislation to stop drilling in all National Forests.

 It only takes a second for Oil & Gas to destroy our 'Protected NAtional Forests' and it only takes a second to sign the petition against their destruction.


Thank you!

Tuesday, September 27, 2011

Radioactive Tracer Patent - Used in Hydraulic Fracturing

Radioactive tracing with particles


United States Patent
Bandy , et al.
                                             September 7, 1993
There is provided radioactive particles having a ceramic matrix and an element which can be bombarded with neutrons to produce a gamma ray-emitting isotope. The particles are manufactured by mixing the ceramic components and the element, forming particles, sintering the particles, and the particles are subsequently made radioactive by bombardment with neutrons. Particles injected into wells or flow apparatus are traced by adding the radioactive particles and detecting the radioactive particles with gamma ray-sensitive instruments. Particles containing different elements are detected by spectral analysis of gamma rays.

Inventors: Bandy; Thomas R. (Katy, TX), Read; Donna A. (Houston, TX), Wallace; Edward S. (Englewood, CO)
Assignee:Protechnics International, Inc. (Houston, TX)
Appl. No.: 07/792,809
Filed: November 15, 1991

Related U.S. Patent Documents

Application NumberFiling DatePatent NumberIssue Date
666044Mar., 19915182051
466238Jan., 1990

Current U.S. Class:250/260 ; 250/259; 250/356.1; 250/356.2
Current International Class: C09K 8/60 (20060101); C09K 8/80 (20060101); E21B 43/267 (20060101); E21B 47/00 (20060101); E21B 47/10 (20060101); E21B 43/25 (20060101); G21G 4/00 (20060101); G21G 4/04 (20060101); G01V 005/00 ()
Field of Search: 250/259,260,356.2,356.1

U.S. Patent Documents

<>Other References<>

Brochure "Tracerscan Service", Halliburton Logging Services, Inc., 1990. .
Article "Tracer Technology Finds Expanding Applications", Petroleum Engineer International, Jun. 1989. .
Brochure "Macrolite Ceramic Spheres", 3M Industrial Mineral Products Div., St. Paul, Minn., Jan. 1, 1990. .
Article "Tracers Can Improve Hydraulic Fracturing" Petroleum Engineer International, Jun. 1989. .
Article "Improved Evaluation Techniques for Multiple Radioactive Tracer Applications", 12th Internatinal Logging Sym. of SAID Paris, France, Oct. 1989..

Primary Examiner: Fields; Carolyn E.
Attorney, Agent or Firm: Pravel, Hewitt, Kimball & Krieger

Parent Case Text

This is a division of application Ser. No. 07/666,044 filed Mar. 7, 1991, now U.S. Pat. No. 5,182,051, which is a continuation-in-part of U.S. Ser. No. 07/466,238, filed Jan. 17, 1990, now abandoned.


What we claim is:

1. A method of locating particles pumped into a well drilled through a subterranean formation comprising:

(a) forming a mixture of (1) an element which when bombarded with neutrons forms a gamma ray-emitting isotope and (2) a ceramic material which when properly processed forms a ceramic particle;

(b) forming particles of the mixture;

(c) irradiating the particles with neutrons to form radioactive particles;

(d) adding the particles to a fluid before the fluid is injected into a well at a concentration effective to allow subsequent detection;

(e) injecting the fluid and the particles into a well; and

(f) logging the well with an instrument capable of detecting the radioactive particles to determine the location of the particles in and around the well.

2. The method of claim 1 wherein the radioactive particles are added to the fluid in a concentration range from about 0.1 ml/1000 gallons to about 10 ml/1000 gallons.

3. The method of claim 1 wherein the instrument used in step (f) is capable of detecting the spectrum of energies of gamma rays emitted by the isotope of the element in the radioactive particles.

4. A method of tracing particles by providing in a fluid particles traceable by radioactivity, said method comprising adding particles to said fluid wherein said particles are comprised of a sintered ceramic material having embedded therein a target element, said target element being non-radioactive until said particles are bombarded with neutrons, and thereafter employing apparatus to detect radioactivity from said particles to determine the location of the particles.

5. A method as defined in claim 4 wherein said particles are bombarded with neutrons after said particles are added to said fluid.

6. A method as defined in claim 4 wherein differing particles having differing target elements are added to said fluid.

7. A method as defined in claim 4 wherein said particles are added to said fluid in a range of concentration from about 0.1 ml/1000 gallons to about 10 ml/1000 gallons.

8. A method as defined in claim 4 wherein said target element is present in said particles at a concentration in the range from an amount detectable by said apparatus to about 5 percent weight.

9. A method as defined in claim 4 wherein said fluid is a slurry.

10. A method as defined in claim 9 wherein the specific gravity of said particles is selected to match approximately the specific gravity of particles in said slurry.

11. A method of treating a well drilled through a subterranean formation comprising introducing a slurry into said well, said slurry having suspended therein particles, said particles being comprised of a sintered ceramic material having embedded therein a target element, said target element being non-radioactive until said particles are bombarded with neutrons.

12. A method as defined in claim 11 wherein said method of treating said well is hydraulic fracturing.

13. A method as defined in claim 11 wherein said method of treating said well is gravel packing.

14. A method as defined in claim 11 wherein particles having differing target elements are introduced into said well at differing times.

15. A method of locating particles in and near a well comprising logging said well using logging apparatus capable of detecting radioactivity and thereby determining the proximity of said particles to said logging apparatus, said well having been treated with a fluid having suspended therein particles, said particles comprising a sintered ceramic material having embedded therein a target element, said target element being non-radioactive until said particles are bombarded with neutrons.

16. A method as defined in claim 15 wherein said target element is present in said particles at a concentration in the range from an amount detectable by said logging apparatus to about 5 percent by weight.

17. A method of treating a well drilled through a subterranean formation comprising introducing a cement slurry into said well, said cement slurry having suspended therein particles, said particles being comprised of a sintered ceramic material having embedded therein a target element, said target element being non-radioactive until said particles are bombarded with neutrons.

18. The method as defined in claim 17 wherein said particles are bombarded with neutrons before said cement slurry is introduced into said well.

19. The method as defined in claim 17 wherein said particles are bombarded with neutrons after said cement slurry is introduced into said well.



1. Field of the Invention

This invention relates to radioactive isotope tracers and methods for their use and manufacture. In one aspect, sintered ceramic particles containing an element having the capability to be made radioactive are provided. In another aspect,radioactive sintered ceramic particles are provided. In still another aspect, a method of manufacturing radioactive particles is provided. In still another aspect, a method of using radioactive particles to locate particles in a wellbore or other piping system with negligible contamination of the system with radioactivity is disclosed.

2. Description of Related Art

Radioactive elements are commonly used for tracing the flow of liquids and solids in flow streams. The elements can be present as a soluble compound in a liquid, as insoluble or slightly soluble particles of the element or a compound of the element suspended in the flow stream, or as a soluble or insoluble compound attached to particles of other material which are suspended in a liquid or gas.

Slurries of particles are pumped into wells drilled through subterranean formations for several reasons. One reason is in connection with hydraulic fracturing of wells. The particles are called "proppant," and such particles function to fill the fracture created in the earth around a well and thereby to allow greater fluid flow rate into or out of the well. It is desirable to know after a well has been fractured the vertical extent of the proppant particles that have been placed around the well--particularly, whether the proppant is located in a zone of the well containing hydrocarbons or whether the proppant has been transported to another zone above or below the hydrocarbon-containing zone. It is common for radioactive particles to be added to the proppant as it is injected into the well. After the fracturing operation is complete, a logging tool is run into the well and the location of the proppant-radioactive particle mixture is located.

Slurries are also used in a well for cementing the casing in the well. The cement slurry is pumped into the well through the casing and flows upward outside the casing. It is important to know where the cement is located outside the casing in the well after it sets. Radioactive tracers are sometimes added to the cement slurry as it is pumped into a well. After the cement has set, a logging tool which measures gamma ray radiation is run into the well and the level of radiation is measured at different depths in the casing of the well. Different radioisotopes may be added to different portions of the cement slurry and the logging tool may be used to measure the location of the different tracers outside the casing. A spectral log may be used to indicate the distance of the tracer from the wellbore.

Another use of slurries in wells is in the process of gravel packing of wells, In this process particles, called "gravel," are placed near the wellbore and in the wellbore outside a screen to prevent formation solids from entering the wellbore or plugging the screen. It is important to know whether the gravel pack is continuous and how far it extends vertically in the well. Radioactive particles are added to the gravel as it is pumped into the well and a logging tool is run into the well after the gravel packing operations are complete to determine the location of the gravel.

Radioactive tracers are used in many other flow systems for measuring flow rates, flow patterns and other phenomena associated with movement of fluids or solids in industry or science. In many of these applications the radioactive tracers are placed directly in a liquid. There is often difficulty from the radioactive material plating on to surfaces or being disseminated through the flow system to contaminate the system with radioactivity.

U.S. Pat. No. 3,492,147 discloses a process for production of resin-coated solids, the resin coating incorporating radioactive materials. U.S. Pat. No. 4,731,531 discloses the use of particulate material which is nonradioactive until it is irradiated by neutrons at the surface of a well immediately before it is injected into the well or after it has been deposited in the formation around the well. The nonradioactive isotope is contained in an infusible resin coated on the surface of the particles. Radioactive particles having an infusible resin on the surface were sold by Halliburton Company under the trademark RAYFRAC.RTM.. Other radioactive particles sold for use in the oil industry are believed to be manufactured by simply immersing sand particles in a radioactive solution and drying the particles, the radioactivity then being trapped within natural cracks existing in the sand particles.

Techniques for detecting and measuring radioactivity are well known. A device such as a Geiger Counter will measure total radioactivity. Techniques for measuring the amount of radiation as a function of the energy of the gamma ray are also well known. Each radioactive isotope emits a characteristic spectrum of energies of radiation. Spectral analysis of the gamma rays from a radioactive isotope of an element used in the laboratory and surface facilities is well-known. In recent years, toolshave been developed and made available for measuring the spectral analysis of gamma rays in wells. Spectral analysis makes possible use of multiple radioactive tracers in a flow system or well at the same time. In addition, technology has been developed to determine the relative distance from the detecting tool of different tracers, based on the phenomenon of Compton scattering of the gamma rays. One system for use in wells is sold by Halliburton Logging Services, Inc. under the trademark TRACERSCAN. This same detection technology could be used in other flow systems. The spectral log in a well makes possible both the vertical and radial distribution of tracers used in evaluating the effectiveness of hydraulic fracturing, cementing, and gravel packing operations. The article "Tracer Technology Finds Expanding Applications," Petroleum Engineer International, June, 1989, pp. 31-36, and references cited therein describe the new spectral analysis technology and its application to wells.

In the application of radiotracers in wells, preferably no tracers are left inside the casing, since only tagged material outside the casing contributes useful information regarding material placement within the formation. A severe limitation in using prior art radioactive particles which are initially radioactive or which are made radioactive by neutron bombardment before injection into a well or piping system is that radioactive material washes off particles or is abraded or is broken from the surface of the particles as they are pumped in a flow stream. This loss of radioactivity from the particles creates a background radiation at certain locations or throughout the well or piping system. The extraneous source of radiation can be a severe limitation in subsequent radioactive logging of wells and greatly diminishes the accuracy of measurements intended to be indicative of conditions outside the wellbore. In piping systems on the surface of the earth, radioactive contamination can be hazardous and can interfere with other operations.

Therefore, there is a great need for particles that can be made radioactive and particles that are radioactive which can be pumped into wells or other flow streams without loss of radioactivity and contamination of the flow stream. Further, a method of manufacturing such particles which allows incorporation of a variety of elements which can produce distinctive radioactive spectra is needed, and a method of employing these particles to locate slurries which have been injected into wells or other piping systems is needed.


In one embodiment of this invention, sintered ceramic particles which are a precursor to radioactive particles, comprising an element which can be bombarded with neutrons to form an isotope which emits gamma rays, are provided. In another embodiment, radioactive particles are provided. In another embodiment, a method of manufacturing particles specially suited for tracing flow in a fluid or slurry is disclosed. The manufacturing process comprises the steps of mixing in powder form ceramic components and an element which, when bombarded by neutrons forms a radioactive isotope, forming the powder mixture into particles, sintering the particles to produce an effective amount of strength and irradiating the sintered particles with neutrons.

In yet another embodiment, sintered radioactive particles produced by mixing ceramic components and an isotope which can be made radioactive by neutron radiation, which are irradiated by neutrons before use, are added to a non-radioactive slurry as it is pumped into a well. The well is then logged with an instrument which measures the level of radioactivity from the gamma ray emission of the particles. Gamma ray spectra are measured to differentiate tracers when particles containing different elements are injected into the stream at different times. In still another embodiment, particles in surface piping systems are traced using radioactivity measurements. In another embodiment, the precursor particles are bombarded with neutrons after their injection into a well or other flow system.


FIG. 1 is a diagram of steps for use of radioactive particles in a well.


The particles which can be made radioactive of the present invention are particles which contain a target element which is embedded in a sintered ceramic matrix.

The radioactive isotope particles of the present invention are ceramic particles that emit gamma rays to allow their detection by instruments. The particles are made of sintered ceramic components and an element which has been bombarded with neutrons to become a gamma ray-emitting isotope.

The ceramic components are common oxides, normally silica or alumina, but other oxides used in the ceramic art may be used. In the mixtures comprising predominantly silica and alumina, a range of mixtures from pure alumina to predominantly silica can be used. Mixed crystalline materials of silica and alumina such as mullite may be used. The ceramic components are first finely divided or powdered and mixed with the target element. By this technique, the target element can be uniformly distributed through the particle. The structure of the powdered starting materials may still be present in the finished particles, but the particles will have an effective amount of strength resulting from bonding of the original powder of ceramic components which has occurred during the sintering process. Other components may be added to aid sintering and to substantially lower the sintering temperature, such components being well known in the ceramics art.

The sintered matrix of the particles should have sufficient strength to resist breaking when the particles are pumped in a stream of fluid. The amount of strength needed will depend upon their application. If the particles are to be pumped at high flow rates in a slurry, such as in hydraulic fracturing treatments in wells, the particles should be strong enough to prevent breaking at high stress, substantially like the ceramic particles now provided as proppant for this application. For added strength, particles having an alumina content above 30 percent by weight are preferred. Also, sintered particles made from very finely divided powder are higher in strength. Powder less than 25 microns in size is preferred. If the radioactiveparticles are to be incorporated into a flow stream moving at a low speed and without abrasive conditions, much lower strength ceramic particles are acceptable, although high strength will not be a disadvantage. In addition to strength, density and size may be important properties of the ceramic particles to be considered in each application.

The target element added to emit gamma rays is embedded in the matrix of the ceramic materials before sintering. The element is selected based upon several variables. One of the important characteristics is the half-life of the radioactiveisotope produced by neutron bombardment. This property is selected based on the measurements to be made and does not limit this invention. Half-lives of from about two days to about 250 days are commonly used. The energies of the gamma rays emitted by the isotope are also an important factor in selecting the element This is especially true when two or more radioactive isotopes are to be used in the same flow stream, when it is desirable that the energy spectra of the different isotopes not excessively overlap It is preferred that the energy spectrum of the gamma rays of the different isotopes not overlap such that the intensity of the gamma rays from each element can be more accurately measured. Thereby, the concentration of each individual isotope can be measured by spectral analysis of the gamma rays.

The cost and availability of the target element embedded in the ceramic particles is one consideration in the selection of which element to use in a particle Target elements suitable for use in the particles of this invention include gold, iodine, iridium, scandium, antimony, silver, hafnium, zirconium, rubidium, chromium, iron, strontium, cobalt, and zinc. Preferred target elements are antimony, iridium, scandium, silver, and hafnium. Most preferred are iridium and scandium.

The target element may be present in its elemental form or as a compound. Compounds of elements useful in this invention are commonly salts or oxides. Iridium oxide is available as a black powder known as "iridium black ". Hafnium oxide is available in pure form Antimony bromide is available is very pure form as crystals. Other compounds of the element may be used, but oxides and salts are readily available. The compound should be stable at the high temperature of processing of the ceramic particle, such that sublimation does not deplete the particles of the compound. The temperature of sintering the particles will normally be above the melting point of the compound of the element.

The concentration of the element in the ceramic particle will depend on the application of the particles, but an effective amount will be less than 5 percent of the weight of the particle, preferably less than 1 percent and most preferably less than 0.5 percent by weight.

Sizes of the particles will normally range from about 8 mesh to about 400 mesh. Particles of a wide range of sizes can be separated into desired sizes by sieving or other particle size separation techniques.

Specific gravity of the particles will range from about 0.5 gm/cc to about 3.9 gm/cc. Particles of different densities can be made and separated by density using well known particle separation techniques.

Radioactive ceramic particles may be manufactured by methods known in the ceramic industry for manufacturing proppants for use in hydraulic fracturing of wells or for manufacturing synthetic gravel for use in gravel packing of wells. Such ceramic particles for proppants are manufactured and used for their strength, their density and their sphericity. U.S. Pat. 4,668,645 discloses a particle for use as a proppant and a method of manufacturing such particles. U.S. Pat. No. 4,068,718 discloses the use of high strength and high density bauxite-containing particles for use as a proppant in wells and describes the methods of manufacture of such particles. The two aforesaid U.S. patents are incorporated herein for all purposes.

Other methods for manufacturing sintered ceramic particles from powder, employing a variety of grinding, mixing, pelletizing and sintering techniques can be used. Ceramic particles of various densities and strengths can be made by mixtures of the oxides of aluminum, silicon, iron, magnesium and other minerals. Ceramic particles made for use as proppants or in gravel packing are manufactured by grinding the ceramic components to fine particle sizes, preferably less than 25 micron particle size, forming a paste of the finely ground material, forming the paste into rounded particles with pelletizing equipment and then sintering the particles. Such particles are sold by Norton Alcoa Proppants of Dallas, Tex. and by Carbo Ceramics Company of Dallas, Tex. We have discovered that the ceramic components of such particles can be mixed with an element which, when bombarded with neutrons, forms a gamma ray emitting isotope, to produce a radioactive particle which has essentially the properties of the ceramic particle not containing the element. Such particles have high strength and resistance to crushing, and can be pumped into a variety of fluid streams without loss of radioactive material to the fluid stream and the conduits for the stream.

MACROLITE.RTM. ceramic spheres sold by 3M Company of St. Paul, Minn. are made from a ceramic powder to have void spaces and specific gravities as low as about 0.58 gm/cc. The particles of this invention can be manufactured by incorporating a target element into the ceramic materials of MACROLITE.RTM. ceramic spheres before they are formed.

It is advantageous to use elements which are not radioactive during formation of the particles, so that health hazards from radioactive materials are avoided during manufacture of the particles. This is an important feature of our invention.

After the particles to be made radioactive, i.e. the precursor radioactive particles, are formed and sintered, the particles may be injected into a flow system or the particles may be transported to a nuclear reactor and radiated with neutrons such that the element present forms a radioactive isotope of that element. The equation given below describes the level of activity resulting from neutron radiation:


A=Activity in millicuries

N.sub.L =6.022.times.10.sup.23

h=Isotopic Abundance

X.sub.sect =Neutron Capture Cross Section

g=Target element mass in grams

t.sub.1/2 =Half life of produced nuclide in seconds

N.sub.f =Neutron flux (neutron cm.sup.-2 sec.sup.-1)

M=Target nuclide atomic weight in grams

t=Neutron bombardment time in seconds.

Activity produced is directly proportional to neutron bombardment time, neutron flux and target element mass. Once an element has been selected for its half-life of radioactivity and its desirable gamma ray spectrum, the concentration of the element needed to seed the particles and the neutron bombardment time can be calculated for a certain location in a certain nuclear reactor having a known neutron flux rate at different locations. The costs of the element and the neutron irradiation are selected to minimize the total cost of producing particles having an effective level of radioactivity.

The selected amount of the target element is added to a suitable amount of ceramic powder which is to be formed into particles, such that the amount of powder to be irradiated, stored and injected into a stream is convenient for the irradiation facility, storage facilities and pumping equipment available for injecting the radioactive powder.

Twenty millicuries of radioactivity is a common amount of radioactivity to transport in one batch. Therefore, this amount of radioactivity will be used as an example. Other amounts, for example 40 millicuries, are often used and the same principles are applicable. The equation above shows, for example, that if 20 millicuries of radioactivity from iridium-192 is to be produced, and the nuclear reactor produces a flux in the cans to be used in the reactor of 5.times.10.sup.12 neutrons cm.sup.-2 sec.sup.-1, 11.5 milligrams of iridium is needed for a bombardment time of 96 hours. This amount of iridium in the form of iridium black is added to a measured amount of ceramic powder, thoroughly mixed and blended, and formed into particles which are then sintered in accord with known techniques for producing sintered particles. The equation shows that if the amount of target element is doubled the amount of bombardment time can be halved. Therefore, the cost of producing particles having differing amounts of target elements can readily be determined, depending on the cost of the element and the cost of irradiation time. For many elements to be made radioactive, the lowest cost of radioactivity will be obtained with the largest amount of the target element in the ceramic particles. Then the highest limiting concentration of the element is determined by that concentration which changes the physical properties of strength or specific gravity of the ceramic particles into an unacceptable range of the property. Tests should be performed to determine the maximum acceptable concentration of target element by mixing various concentrations of element and ceramic components, sintering the particles and measuring the desired property. Specific gravity of particles may be measured by well known methods. Strength may be measured by crush tests of packed beds of particles or by individual particles strength tests which are well known for testing proppant particles.

For some applications, only a small amount of particles is needed to contain 20 millicuries of radioactivity. But, it is possible to vary the concentration of target element in the ceramic over a wide range of concentrations. The lowest practical level of concentration will normally be determined by the volume available in the reactor used for irradiation or by the pump used to meter the particles into the stream where they will be used. For particles to be used in hydraulic fracturing, 20 millicuries of activity will preferably be contained in a volume of particles in the range from about 5 milliliters to about 100 milliliters of particles. Much larger amounts of particles could be used to contain the radioactivity, but the minimum concentration of target element in the ceramic will usually be determined by the pumping apparatus used to add the particles to a stream and the volume limitations of the reactor used for irradiation of the particles. Small volumes of particles can be used when accurate means are available for metering small amounts of particles into a stream. Radioactivity levels in the range from about 0.02 to about 20.0 millicuries per milliliter of particles are suitable. Preferably, the radioactivity level is in the range from about 0.2 to about 4.0 millicuries per milliliter of particles.

After the particles are radiated with neutrons, their manufacture is complete. The particles must then be handled as radioactive sources. Well known techniques are used for protecting personnel from exposure to gamma rays emitted from the particles.

Radioactive particles are added to a fluid which is being pumped into a well or are added to a fluid passing through surface piping or equipment for other applications by first mixing the radioactive particles with fluid to form a concentrated slurry. The liquid of the slurry may be viscosified by polymers. The slurry of radioactive particles is stored in a small closed radioactive materials reservoir. The reservoir may contain an agitator to keep the radioactive particles in suspension. The slurry is pumped from the reservoir into the low-pressure section of the flow stream to be traced with a low pressure pump such as a peristaltic pump. A high-pressure positive displacement pump can be used when the particles are injected into a high-pressure stream. The concentration of radioactive particles in the concentrated slurry or radioactive particles is usually in the range of about 10 grams to about 1000 grams per gallon of slurry.

Referring to FIG. 1, in one embodiment of this invention particles are formed from a mixture of a ceramic material and a selected element which, when bombarded with neutrons, forms a gamma ray-emitting isotope, the particles are then irradiated with neutrons to form radioactive particles, the particles are added to a fluid before the fluid is injected into a well, the fluid is injected into a well, and afterward the well is logged with an instrument capable of detecting the radioactiveparticles.

For most applications in wells, the slurry of radioactive particles is pumped out of the reservoir and into the stream at a rate such that 20 millicuries is used to trace from about 10,000 to about 100,000 pounds of solid particles or about 10,000 to about 100,000 gallons of fluid The activity level may vary in the range from about 0.1 to about 10 millicuries per thousand gallons of fluid or thousand pounds of solids. This amount of radioactivity is preferably contained in a volume of particles from about 5 cc to about 100 cc, but much larger volumes of particles may be used with a suitable pump for pumping the slurry of radioactive particles. If this amount of radioactivity is contained in a larger volume of particles, theradioactive particles will either contain a proportionately lower concentration of target element or the particles will be irradiated with neutrons for a proportionately smaller time.

Preferably, the radioactive particles have about the same size and specific gravity as the nonradioactive particles in the flow stream when applied to tracing the particles in hydraulic fracturing and gravel packing operations. The particles should be small enough to produce low settling rates when used in cement slurries. For other types of fluids, the size and specific gravity will be selected to accomplish the purpose of the tracing application. For example, particles less than a certain size may be sieved from a mixture of sizes and added to a flow stream to determine the size of constrictions in the flow stream. Other applications dependent on size and specific gravity will be obvious to users of the particles.

Specific gravity of the particles can be varied to be compatible with the application. The ceramic particles produced for hydraulic fracturing of wells vary in specific gravity from about 2.6 gm/cc to about 3.8 gm/cc. The density of these particles will not be significantly changed when the element to be made radioactive is embedded into the particles. Preferably, radioactive particles will be made to have approximately the same density as the non-radioactive particles with which they are used. Particles sold by 3M Company under the trademark MACROLITE.RTM. may have a specific gravity as low as 0.58 gm/cc. Again, preferably the radioactive particles will be made to approximately match the density of the non-radioactive particles. Strength of the particles will also vary with specific gravity, but even the relatively low strength of these low specific gravity particles will adequate for gravel packing applications. Other applications not requiring high-strength can also use the low specific gravity particles. To avoid breaking and abrasion of particles, which can lead to loss of radioactivity from the particles, strength is preferably as high as consistent with other properties of the particles.

After the radioactive particles are pumped into a well and out of the casing of the well so that they are no longer in the wellbore, a logging instrument is lowered into the well which is capable of detecting the gamma rays emitted by the isotope of the element. The gamma rays are capable of penetrating at least several inches of the earth surrounding the well and of penetrating the casing in the well. The gamma rays specific to the isotope of the element may be detected by performing an analysis of the energy of the gamma rays detected by the logging tool. A spectrum of energy of gamma rays characteristic of each radioactive element present is obtained. Techniques are used for determining, based on differing attenuation by Compton scattering of gamma rays having differing energy levels, the amount of gamma radiation coming from inside the wellbore, which would result from radioactive material lost from the particles during flow down the wellbore.

Ceramic particles containing different target elements may be used at the same time or at different times in the pumping operation, may have different specific gravity or may have different size. The locations of the particles having different target elements are then determined with the gamma ray detector.

In gravel packing operations, the radioactive particles may be inside the casing and outside a screen or other type filter in the wellbore. In this application, also, the logging tool is surrounded by the radioactive particles.

In a flow stream or other surface apparatus, the gamma ray detection instrument is located in the vicinity of the radioactive particles to detect the gamma rays. Particle location of particles containing different target elements, which may also have different sizes and specific gravities, can be determined by spectral analysis of the gamma rays.

The applications described above assumed that the particles had been irradiated by neutrons before injection into the well or flow stream. It should be understood that the precursor particles, obtained after sintering and before irradiation with neutrons, can be used in all applications if a neutron source is applied to the particles after they are in the flow stream or well. The particles of this invention will be stable to their environment of use, and can be irradiated or re-irradiated long after the time they are injected into a flow stream or well.


Ceramic particles containing iridium were manufactured. The procedures normally used for manufacturing a ceramic proppant particle containing primarily alumina and silica and smaller amounts of other oxide minerals were used. The ceramic materials were finely ground. About 20 grams of iridium black, available from Aldrich Chemical Company, was thoroughly mixed with 30,418 grams of the ceramic powder. The powdered mixture was then formed into a paste containing chemical binders. The paste was formed into approximately spherical particles. The ceramic materials are said to be "green" at this stage. The green ceramic particles were then sintered by firing in an oven at a temperature in the range of about to 1500 .degree. C. The particles containing the iridium were essentially the same density and crush resistance as the particles of high strength ceramic material without the iridium. The size range of the particles was from about 20 mesh to about 40 mesh.

A portion of the particles containing iridium was then placed in a nuclear reactor for a period of 42 hours. A volume of 15 milliliters of particles was irradiated at a neutron flux of 9.times.10.sup.12 neutrons cm.sup.-2 sec.sup.-1. At the end of irradiation, the activity of the particles was measured to be about 20 millicuries. The activity calculated from above equation was 20.7 millicuries.

The radioactive particles are transported to a well where hydraulic fracturing operations are performed. Fracturing fluid is pumped down the casing of the well and through perforations. Sand in the size range 20-40 mesh is used as proppant. Radioactive ceramic particles manufactured according to the methods described herein are added to the fluid along with the sand at an appropriate time. The ceramic radioactive particles have about the density of sand and are 20-40 mesh size. After these fracturing operations are complete, the well is logged with the TRACERSCAN system. Results of the log show that gamma ray radiation from iridium is present only near the perforations. The very low level of radioactivity in the wellbore above the perforations shows that loss of radioactive iridium material from the particles during the operations is negligible.

The invention has been described with reference to its preferred embodiments. Those of ordinary skill in the art may, upon reading this disclosure, appreciate changes or modifications which do not depart from the scope and spirit of the invention as described above or claimed hereafter.

* * * * *

In North Dakota, Flames of Wasted Natural Gas Light the Prairie

Jim Wilson/The New York Times
Thirty percent of the natural gas extracted in North Dakota is flared off, like this gas near Ray. More Photos »

Every day, more than 100 million cubic feet of natural gas is flared this way — enough energy to heat half a million homes for a day.

The flared gas also spews at least two million tons of carbon dioxide into the atmosphere every year, as much as 384,000 cars or a medium-size coal-fired power plant would emit, alarming some environmentalists.

All told, 30 percent of the natural gas produced in North Dakota is burned as waste. No other major domestic oil field currently flares close to that much, though the practice is still common in countries like Russia, Nigeria and Iran.

With few government regulations that limit the flaring, more burning is also taking place in the Eagle Ford shale field in Texas, and some environmentalists and industry executives say that it could happen in Oklahoma, Arkansas and Ohio, too, as drilling expands in new fields there unlocked by techniques like hydraulic fracturing and horizontal drilling.

“North Dakota is not as bad as Kazakhstan, but this is not what you would expect a civilized, efficient society to do: to flare off a perfectly good product just because it’s expensive to bring to market,” said Michael E. Webber, associate director of the Center for International Energy and Environmental Policy at the University of Texas at Austin.

Save The Poudre Requests Analysis Of NISP Water Used For Oil And Gas Drilling And Fracking


September 26, 2011
Contact: Gary Wockner, Save the Poudre: Poudre Waterkeeper, 970-218-8310

Save The Poudre Requests Analysis Of NISP Water Used For Oil And Gas Drilling And Fracking
Fort Collins, CO -- Today Save the Poudre sent a letter to the U.S. Army Corps of Engineers requesting that the Supplemental Draft Environmental Impact Statement (SDEIS) for the Northern Integrated Supply Project (NISP) contain an analysis of how NISP water would be used for oil and gas drilling and fracking. Records requested by Save the Poudre have revealed that some NISP communities are already selling water for drilling and fracking. Due to the extensive oil and gas boom in Weld County, it is very likely that NISP water would be used for drilling and fracking if NISP were ever built.

The letter is here:

 "Some NISP towns are selling water for drilling and fracking," said Gary Wockner of Save the Poudre. "The Supplemental Draft Environmental Impact Statement for NISP must analyze the potential use of NISP water for drilling and fracking including the extent of that use, the impacts to water rights and stream flows, and the impacts to the environment."

Records reveal that millions of gallons of water have been sold for drilling and fracking by NISP towns. Nine of the fifteen NISP participants are in Weld County where nearly 18,000 active oil and gas wells are producing. Industry experts predict that up to 10,000 more wells will be drilled in the Weld County over the next decade.

NISP is now at least 6 years late and at least $150 million over budget. In early 2011, the SDEIS was delayed for the third time with the Army Corps of Engineers saying the SDEIS will be released sometime in 2012.


Click images to enlarge

"Halliburton doesn't use radioactive tracers," Ramurthy said. "That's another company." - NOT SO FAST

Halliburton's use of Radioactive Tracers -  Sept 27, 2011

Weston Wilson, a former U.S. Environmental Protection Agency environmental engineer in Denver, asked Ramurthy if Halliburton uses radioactive tracer chemicals in its fracking fluids.

"Halliburton doesn't use radioactive tracers," Ramurthy said. "That's another company."

TracerScanSM Radioactive Tracer Log Service

Tracking Tracers Yields a Range of Formation Answers
The TracerScanSMreal-time logging service identifies individual radioactive tracers in multiple-tracer operations, determines their vertical and radial distributions, and accurately distinguishes tracers in the borehole from tracers in the formation.
With the TracerScan service, operators can simultaneously estimate natural gamma ray background for more reliable tracer data. Only one run is required after tracer placement because TracerScan service measures gamma ray spectra rather than tracer half-life. The technique also results in environmental benefits because tracers with a short half-life rapidly decay to environmentally safe levels.

For hydraulic fracturing operations, TracerScan service identifies fractured and propped intervals to determine if the tagged materials were pumped away from the wellbore as desired (see image). TracerScan™ logs monitor the effects of tagged acid jobs and allow the dissolution of the rock matrix. A relative distance calculation reveals the radial distribution of the cement and verifies that channels have been closed. The relative distance calculation also confirms placement of tagged packing materials in FracPac™ and gravel pack operations.


Following FracPac stimulation, wireline logs can be run to help evaluate treatment effectiveness. Logs can determine the height of hydraulically induced fractures, verify the placement of pack materials, and analyze flow from treated formations. Tracer and production logs are the wireline services most commonly used for FracPac evaluation.

To verify the placement of pumped materials such as fracturing fluid, proppant, and gravel, spectral gamma ray tools such as Halliburton’s TracerScan tool are used. The materials to be pumped are tagged with radioactive tracers that have dissimilar gamma ray spectra. Each tracer emits gamma rays of different energies and different intensities than the other tracers. In a FracPac job, the fracturing fluid may be tagged with one tracer, the proppant with a second tracer, and the gravel with a third tracer. Since the TracerScan tool can distinguish gamma rays in different energy ranges, it can differentiate the tracers after they have been pumped downhole during FracPac operations.

TracerScan logs record spectral gamma ray data as a function of depth and therefore can evaluate the vertical distribution of the tagged materials. This allows the total and propped fracture heights to be estimated and voids in gravel packs to be located.
TracerScan data also give information regarding the approximate radial location of tracers and permits tracers in the borehole to be distinguished from tracers in the formation are at some distance from the wellbore, high-energy tracers (those with most gamma ray energies exceeding 600 keV) are more easily detected than are low-energy tracers. Thus, high-energy tracers, especially those with energies above 1,000 keV, are more suitable for tagging materials used during the early stages of fracturing operations. Table 15.1 gives energy levels and half-lives of several tracers used in evaluating fracturing and gravel packing operations.

TRACER SPECTRAL PEAKS – When more than one tracer is used, the gamma ray spectra of the tracers must be considered. The major gamma ray peaks in each spectrum must be sufficiently different from those in the other spectra so that the tracers can be easily distinguished from one another. One of these combinations is suitable for TracerScan work, and the other is not.

NUMBER OF TRACERS – In general, the minimum number of tracers should be used to evaluate the FracPac treatment. As the number of isotopes that are used increases, it becomes more difficult to spectrally differentiate the isotopes. It also becomes more difficult to determine precisely the concentrations and the radial-distance indicators.

TRACER HALF-LIVES – Tracer half-lives should be long enough so that if there are reasonable job delays, it should not be necessary to obtain additional tracers. Tracers with half-lives on the order of 60 days are commonly used, but specific jobs may require shorter or longer times.

TRACER TYPES – In 1992, TracerScan log interpretation was enhanced by the introduction of zero-wash tracers, also known as zero-leach tracers. Before zero-wash tracers became available, tracers were prone to wash off the tagged material or to plate out on tubular assemblies. This caused abnormally high tracer concentrations in the borehole. The new technology has eliminated the wash-off and plating tendency for solid tracers; however, except for scandium, liquid tracers still exhibit this characteristic. Nevertheless, liquid tracers can be used successfully, but it is critical that the tagging agent be chemically formulated so that preferential deposition of the tracer will occur in the formation and not in the borehole.


TRACER CONCENTRATIONS – There is a natural variation in the intensity of gamma rays emitted by tracers; thus, TracerScan measurements will exhibit statistical variations. Tracer concentrations on tagged materials must be high enough to minimize these statistical variations in TracerScan measurements but must be low enough to not distort tool response. Spectral gamma ray tools are designed for a linear response up to a certain maximum gamma counting rate (generally between 2,000 and 5,000 API units); higher rates degrade the response.

Tracer injection rates are commonly a few tenths of a millicurie per 1,000 gallons of fluid (a few megaBecquerels per cubic meter of fluid, or a few hundredths of a megaBecquerel per kilogram of solid). These rates usually result in gamma ray measurements ofa few hundred to a few thousand API units.
Since the gravel is concentrated in the borehole and the fracturing fluid and proppant are dispersed in the formation, care must be taken in selecting the tracers and their concentrations so that gamma rays from tracers in the formation are not obscured by gamma rays from tracers in the borehole. It is also important that the tagged components of the FracPac job be pumped in a manner that is representative of the FracPac operation as a whole.


Data Quality Considerations

Several measures can be taken to ensure that the information obtained from TracerScan logs is of the highest quality possible. In general, these measures increase the accuracy of measured data and reduce the number of interpretation possibilities. First, information from other logs, especially gamma ray and sonic, is helpful. Although not required, a TracerScan log can be run before a FracPac job to measure the background gamma radiation that must be subtracted from the later tracer measurements.

When such a prejob TracerScan log is not run, the background gamma ray is estimated from the post job log.