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Determination of Mercury in Aqueous and Geologic Materials by Continuous Flow-Cold Vapor-Atomic Fluorescence Spectrometry (CVAFS)

New methods for the determination of total mercury in geologic materials and dissolved mercury in aqueous samples have been developed that will replace the methods currently (2006) in use. The new methods eliminate the use of sodium dichromate (Na2Cr2O7 ?2H2O) as an oxidizer and preservative and significantly lower the detection limit for geologic and aqueous samples. The new methods also update instrumentation from the traditional use of cold vapor-atomic absorption spectrometry to cold vapor-atomic fluorescence spectrometry. At the same time, the new digestion procedures for geologic materials use the same size test tubes, and the same aluminum heating block and hot plate as required by the current methods. New procedures for collecting and processing of aqueous samples use the same procedures that are currently (2006) in use except that the samples are now preserved with concentrated hydrochloric acid/bromine monochloride instead of sodium dichromate/nitric acid. Both the 'old' and new methods have the same analyst productivity rates. These similarities should permit easy migration to the new methods. Analysis of geologic and aqueous reference standards using the new methods show that these procedures provide mercury recoveries that are as good as or better than the previously used methods.

Techniques and Methods

Borehole geophysics applied to ground-water investigations

The purpose of this manual is to provide hydrologists, geologists, and others who have the necessary background in hydrogeology with the basic information needed to apply the most useful borehole-geophysical-logging techniques to the solution of problems in ground-water hydrology. Geophysical logs can provide information on the construction of wells and on the character of the rocks and fluids penetrated by those wells, as well as on changes in the character of these factors over time. The response of well logs is caused by petrophysical factors, by the quality, temperature, and pressure of interstitial fluids, and by ground-water flow. Qualitative and quantitative analysis of analog records and computer analysis of digitized logs are used to derive geohydrologic information. This information can then be extrapolated vertically within a well and laterally to other wells using logs. The physical principles by which the mechanical and electronic components of a logging system measure properties of rocks, fluids, and wells, as well as the principles of measurement, must be understood if geophysical logs are to be interpreted correctly. Plating a logging operation involves selecting the equipment and the logs most likely to provide the needed information. Information on well construction and geohydrology is needed to guide this selection. Quality control of logs is an important responsibility of both the equipment operator and the log analyst and requires both calibration and well-site standardization of equipment. Logging techniques that are widely used in ground-water hydrology or that have significant potential for application to this field include spontaneous potential, resistance, resistivity, gamma, gamma spectrometry, gamma-gamma, neutron, acoustic velocity, acoustic televiewer, caliper, and fluid temperature, conductivity, and flow. The following topics are discussed for each of these techniques: principles and instrumentation, calibration and standardization, volume of investigation, extraneous effects, and interpretation and applications.

Techniques of Water-Resources Investigations

Determination of minor elements in water by emission spectroscopy

With the emission spectrograph, the analyst is able to determine many minor elements simultaneously in water samples. Spectrographic methods differ chiefly in techniques of preconcentrating the elements. For waters with dissolved solids of less than 1,000 milligrams per liter, the method of evaporating to dryness and determining the elements in the dried residue is sensitive, precise, and reasonably accurate. The lower limits of detection vary with the quantity of dissolved solids. Twenty-four elements are determined by this method. For waters with more than 1,000 milligrams per liter of dissolved solids, it is necessary to separate the minor elements from the major constituents before spectrographically determining the former, in order to achieve adequate lower limits of detection. Such procedures generally require more time than the residue method. In the first of two such procedures given, 21 of the metallic elements are precipitated with thioacetamide prior to spectrographic determination. In an alternate procedure, 18 elements are precipitated quantitatively with complexing reagents 8-hydroxyquinoline, tannic acid, and thioanlide. This method is faster than the thioacetamide method, but at the sacrifice of some elements. A Fortran IV computer program for processing densitometric data is given in the section 'Computer Program.'

Techniques of Water-Resources Investigations

Theoretical considerations and a simple method for measuring alkalinity and acidity in low-pH waters by gran titration

Titrations for alkalinity and acidity using the technique described by Gran (1952, Determination of the equivalence point in potentiometric titrations, Part II: The Analyst, v. 77, p. 661-671) have been employed in the analysis of low-pH natural waters. This report includes a synopsis of the theory and calculations associated with Gran's technique and presents a simple and inexpensive method for performing alkalinity and acidity determinations. However, potential sources of error introduced by the chemical character of some waters may limit the utility of Gran's technique. Therefore, the cost- and time-efficient method for performing alkalinity and acidity determinations described in this report is useful for exploring the suitability of Gran's technique in studies of water chemistry.

Water-Resources Investigations Report

Determination of phenoxy acid herbicides in water by electron-capture and microcoulometric gas chromatography

A sensitive gas chromatographic method using microcoulometric titration and electron-capture detection for the analysis of 2,4-D, silvex, 2,4,5-T, and other phenoxy acid herbicides in water is described. The herbicides are extracted from unfiltered water samples (800-1,000 ml) by use of ethyl ether ; then the herbicides are concentrated and esterilied. To allow the analyst a choice, two esterilication procedures--using either boron trifluoride-methanol or diazomethane--are evaluated. Microcoulometric gas chromatography is specific for the detection of halogenated compounds such as the phenoxy acid herbicides whereas it does not respond to nonhalogenated components. Microcoulometric gas chromatography requires care and patience. It is not convenient for rapid screening of l-liter samples that contain less than 1 microgram of the herbicide. Although electroncapture gas chromatography is less selective and more critically affected by interfering substances, it is, nevertheless, convenient and more sensitive than microcoulometric gas chromatography. Two different liquid phases are used in the gas chromatographic columns--DC-200 silicone in one column and QF-1 silicone in the other. The performance of both columns is improved by the addition of Carbowax 20M. The Gas Chrom Q support is coated with the liquid phases by the 'frontal-analysis' technique. The practical lower limits for measurement of the phenoxy acid herbicides in water primarily depend upon the sample size, interferences present, anal instrumentation used. With l-liter samples of water, the practical lower limits of measurement are 10 ppt (parts per trillion) for 2,4-D and 2 ppt for silvex and 2,4,5-T when electron-capture detection is used, and approximately 20 ppt for each herbicide when analyzed by microcoulometric-titration gas chromatography. Recoveries of the herbicides immediately after addition to unfiltered water samples averaged 92 percent for 2,4-D, 90 percent for silvex, and 98 percent for 2,4,5-T. Studies on the stability of herbicides added to water samples showed that 2,4-D may be rapidly degraded, especially if the samples are obtained from areas which have been repeatedly sprayed with 2,4-D. When degradation was observed, added 2,4-D rapidly decomposed within 10 days. At concentrations of about 200 ppt, however, the degradation rate was diminished. In 20 days the concentration of 2,4-D was reduced to 160-180 ppt.

Water Supply Paper

Assessment of thermal maturity trends in Devonian-Mississippian source rocks using Raman spectroscopy: Limitations of peak-fitting method

The thermal maturity of shale is often measured by vitrinite reflectance (VRo). VRo measurements for the Devonian–Mississippian black shale source rocks evaluated herein predicted thermal immaturity in areas where associated reservoir rocks are oil-producing. This limitation of the VRo method led to the current evaluation of Raman spectroscopy as a suitable alternative for developing correlations between thermal maturity and Raman spectra. In this study, Raman spectra of Devonian–Mississippian black shale source rocks were regressed against measured VRo or sample-depth. Attempts were made to develop quantitative correlations of thermal maturity. Using sample-depth as a proxy for thermal maturity is not without limitations as thermal maturity as a function of depth depends on thermal gradient, which can vary through time, subsidence rate, uplift, lack of uplift, and faulting. Correlations between Raman data and vitrinite reflectance or sample-depth were quantified by peak-fitting the spectra. Various peak-fitting procedures were evaluated to determine the effects of the number of peaks and maximum peak widths on correlations between spectral metrics and thermal maturity. Correlations between D-frequency, G-band full width at half maximum (FWHM), and band separation between the G- and D-peaks and thermal maturity provided some degree of linearity throughout most peak-fitting assessments; however, these correlations and those calculated from the G-frequency, D/G FWHM ratio, and D/G peak area ratio also revealed a strong dependence on peak-fitting processes. This dependency on spectral analysis techniques raises questions about the validity of peak-fitting, particularly given the amount of subjective analyst involvement necessary to reconstruct spectra. This research shows how user interpretation and extrapolation affected the comparability of different samples, the accuracy of generated trends, and therefore, the potential of the Raman spectral method to become an industry benchmark as a thermal maturity probe. A Raman method devoid of extensive operator interaction and data manipulation is quintessential for creating a standard method.

Frontiers in Energy Research

Good practices for species distribution modeling of deep-sea corals and sponges for resource management: Data collection, analysis, validation, and communication

Resource managers in the United States and worldwide are tasked with identifying and mitigating trade-offs between human activities in the deep sea (e.g., fishing, energy development, and mining) and their impacts on habitat-forming invertebrates, including deep-sea corals and sponges (DSCS). Related management decisions require information about where DSCS occur and in what densities. Species distribution modeling (SDM) provides a cost-effective means of identifying potential DSCS habitat over large areas to inform these management decisions and data collection. Here we describe good practices for DSCS SDM, especially in the context of data collection and management applications. Managers typically need information regarding DSCS encounter probabilities, densities, and sizes, defined at sub-regional to basin-wide scales and validated using subsequent, targeted data collections. To realistically achieve these goals, we suggest analysts: 1) integrate available data sources in SDMs including fine-scale visual sampling and broad-scale resource surveys (e.g., fisheries trawl surveys); and 2) include environmental predictor variables representing multiple spatial scales, model residual spatial autocorrelation, and quantify prediction uncertainty. When possible, models fitted to presence-absence and density data are preferred over models fitted only to presence data, which are difficult to validate and can confound estimated probability of occurrence or density with sampling effort. Ensembles of models can provide robust predictions, while multi-species models leverage information across taxa and facilitate community inference. To facilitate the use of models by managers, predictions should be expressed in units that are widely understood and validated at an appropriate spatial scale using a sampling design that provides strong statistical inference. We present three case studies for the Pacific Ocean that illustrate good practices with respect to data collection, modeling, and validation; these case studies demonstrate it is possible to implement our good practices in real-world settings.

Frontiers in Marine Science

Statistical facilitation in environmental science: Integrating results from complementary statistical analyses can improve ecological interpretations

Professionals working in biological conservation seek to understand, manage, and restore populations of native organisms using many techniques. A common approach for this discipline is using long-term data collections to inform decision making. However, several quantitative issues complicate statistical analysis of monitoring datasets and can reduce the utility of results for conservation decision making. Integrating results from multiple analyses applied to the same dataset (i.e., approaching the same biological problem using different techniques) is one way to address concerns related to field data that violate statistical assumptions. This process allows data analysts, researchers, and managers to assemble insights based on the weight of evidence. Here we tested whether three different statistical techniques [(1) multiple logistic regression on original data, (2) multiple logistic regression on standardized data (i.e., mean of 0 and standard deviation of 1), and (3) random forest analysis] identified a similar hierarchy for selecting natural and anthropogenic habitat regressors. Our examination of how environmental variables affected Plains Minnow ( Hybognathus placitus ), a state-threatened fish, is relevant to other taxa and locations. We gained useful information from redundancies (i.e., agreements across analyses). New directions also emerged by addressing ambiguities (i.e., disagreements among results across analyses). When multiple analyses were integrated into one ecological story, a clearer interpretation emerged. Viewing different statistical tests as facilitators that provide mutual advantages can advance the understanding and application of statistical analyses applied to non-experimental field datasets.

Kansas

Mapping forest height in Alaska using GLAS, Landsat composites, and airborne LiDAR

Vegetation structure, including forest canopy height, is an important input variable to fire behavior modeling systems for simulating wildfire behavior. As such, forest canopy height is one of a nationwide suite of products generated by the LANDFIRE program. In the past, LANDFIRE has relied on a combination of field observations and Landsat imagery to develop existing vegetation structure products. The paucity of field data in the remote Alaskan forests has led to a very simple forest canopy height classification for the original LANDFIRE forest height map. To better meet the needs of data users and refine the map legend, LANDFIRE incorporated ICESat Geoscience Laser Altimeter System (GLAS) data into the updating process when developing the LANDFIRE 2010 product. The high latitude of this region enabled dense coverage of discrete GLAS samples, from which forest height was calculated. Different methods for deriving height from the GLAS waveform data were applied, including an attempt to correct for slope. These methods were then evaluated and integrated into the final map according to predefined criteria. The resulting map of forest canopy height includes more height classes than the original map, thereby better depicting the heterogeneity of the landscape, and provides seamless data for fire behavior analysts and other users of LANDFIRE data.

Alaska

Critical habitat for ovigerous Dungeness crabs

The Dungeness crab, Cancer magister , supports an important fishery in the northeastern Pacific Ocean, yet there is limited knowledge of ovigerous female brooding locations and brooding behavior. Our earlier research suggests that ovigerous crabs aggregate at the same brooding locations for many years. Within these locations, ovigerous females occur in high densities, with the majority of the aggregation buried within the sediment. These locations often have similar water depths and sediment types and appear to be critical for this life history stage. Our study was designed to examine the bathymetric distribution of Dungeness crabs in bays with and without sea otters at eight locations within the Glacier Bay area by conducting transects with a video-equipped manned submersible. Two of the bays investigated contained large aggregations of ovigerous females. At both sites the substrate was composed primarily of sand. However, only a small percentage of the 33 km of transects were classified as sand. These data suggest that sand substrate may be a limiting resource. Since crab brooding aggregations represent a large portion of the crab population within a small area, and because they are a critical component of Dungeness life history, areas with these characteristics need to be investigated, mapped, and protected from development or exploitation. The areas requiring protection from the impact of anthropogenic wastes, fishing, and logging activities could be quite small, thus limiting conflict with alternative users.

Conference Paper

Detection and characterization of benthic filamentous algal stands ( Cladophora sp.) on rocky substrata using a high-frequency echosounder

A high-frequency echosounder was used to detect and characterize percent cover and stand height of the benthic filamentous green alga Cladophora sp. on rocky substratum of the Laurentian Great Lakes. Comparisons between in situ observations and estimates of the algal stand characteristics (percent cover, stand height) derived from the acoustic data show good agreement for algal stands that exceeded the height threshold for detection by acoustics (~7.5 cm). Backscatter intensity and volume scattering strength were unable to provide any predictive power for estimating algal biomass. A comparative analysis between the only current commercial software (EcoSAV™) and an alternate method using a graphical user interface (GUI) written in MATLAB® confirmed previous findings that EcoSAV functions poorly in conditions where the substrate is uneven and bottom depth changes rapidly. The GUI method uses a signal processing algorithm similar to that of EcoSAV but bases bottom depth classification and algal stand height classification on adjustable thresholds that can be visualized by a trained analyst. This study documents the successful characterization of nuisance quantities of filamentous algae on hard substrate using an acoustic system and demonstrates the potential to significantly increase the efficiency of collecting information on the distribution of nuisance macroalgae. This study also highlights the need for further development of more flexible classification algorithms that can be used in a variety of aquatic ecosystems.

Great Lakes

Resilience thinking and a decision-analytic approach to conservation: strange bedfellows or essential partners?

There has been some tendency to view decision science and resilience theory as opposing approaches, or at least as contending perspectives, for natural resource management. Resilience proponents have been especially critical of optimization in decision science, at least for those cases where it is focused on the aggressive pursuit of efficiency. In general, optimization of resource systems is held to reduce spatial, temporal, or organizational heterogeneity that would otherwise limit efficiency, leading to homogenization of a system and making it less able to cope with unexpected changes or disturbances. For their part, decision analysts have been critical of resilience proponents for not providing much practical advice to decision makers. We believe a key source of tension between resilience thinking and application of decision science is the pursuit of efficiency in the latter (i.e., choosing the “best” management action or strategy option to maximize productivity of one or few resource components), vs. a desire in the former to keep options open (i.e., maintaining and enhancing diversity). It seems obvious, however, that with managed natural systems, there must be a principle by which to guide decision making, which at a minimumallows for a comparison of projected outcomes associated with decision alternatives. This is true even if the primary concern of decision making is the preservation of system resilience. We describe how a careful framing of conservation problems, especially in terms of management objectives and predictive models, can help reduce the purported tension between resiliencethinking and decision analysis. In particular, objective setting in conservation problems needs to be more attuned to the dynamics of ecological systems and to the possibility of deep uncertainties that underlie the risk of unintended, if not irreversible, outcomes. Resilience thinking also leads to the suggestion that model development should focus more on process rather than pattern, on multiple scales of influence, and on phenomena that can create alternative stability regimes. Although we acknowledge the inherent difficulties in modeling ecological processes, we stress that formulation of useful models need not depend on a thorough mechanistic understanding or precise parameterization, assuming that uncertainty is acknowledged and treated in a systematic manner.

Ecology and Society

Using Christmas Bird Count data in analysis of population change

The scientific credibility of Christmas Bird Count (CBC) results depend on the development and implementation of appropriate methods of statistical analysis. The key to any successful analysis of CBC data is to begin with a careful review of how the limitations of the data are likely to influence the results of the analysis, then to choose methods of analysis that accommodate as much as possible the limitations of the survey. For our analyses of CBC data, we develop a flexible model for effort adjustment and use information from the data to guide the selection of the best model. We include geographic structuring to accommodate the regional variation in number of samples, use a model that allows for overdispersed poisson data appropriate for counts, and employ empirical Bayes procedures to accommodate differences in quality of information in regional summaries. This generalized linear model approach is very flexible, and can be applied to a variety of studies focused on factors influencing wintering bird populations. In particular, the model can be easily modified to contain covariates, allowing for assessment of associations between CBC counts and winter weather, disturbance, and a variety of other environmental factors. These new survey analysis methods have added value in that they provide insights into changes in survey design that can enhance the value of the information. The CBC has been extremely successful as a tool for increasing public interest in birding and bird conservation. Use of the information for bird conservation creates new demands on quality of information, and it is important to maintain a dialogue between users of the information, information needs for the analyses, and survey coordinators and participants. Our work as survey analysts emphasizes the value and limitations of existing data, and provides some indications of what features of the survey could be modified to make the survey a more reliable source of bird population data. Surveys only remain useful if they adapt to current needs, while still maintaining consistency with historical goals.

American Birds

Use of the Legal-Institutional Analysis Model to assess hydropower licensing negotiations

In the United States, the Federal Energy Regulatory Commission (FERC) is responsible for issuing or renewing licenses for hydropower projects owned and operated by power companies. During the licensing process, these companies are required to consult with agencies and other parties that are affected by project operating regimes. Typical participants include state and federal fish and wildlife agencies, environmental interest groups, and the FERC. One of the most difficult tasks facing participants is to reach agreement about what kinds of environmental conditions should be placed on license. Researchers at the United States Geological Survey developed a model to analyze the institutional context of natural resource disputes. The Legal-Institutional Analysis Model (LIAM) is a computerized model that allows an analyst to determine the likely behavior of each organization in a conflict. The model also analyzes the types and levels of negotiating power held by each organization. Researchers at the USGS have used the model in several cases involving hydropower license applications. To use the model, they facilitate workshops for stakeholder groups in order to develop a shared understanding of the likely obstacles and opportunities for successful resolution of the issues. This allows a systematic workshop analyses to develop strategies for successful negotiations, because they are able to better understand the negotiation problem and work more effectively with both their allies and their competitors.

Conference Paper

Using open hole and cased-hole resistivity logs to monitor gas hydrate dissociation during a thermal test in the mallik 5L-38 research well, Mackenzie Delta, Canada

Gas hydrates, which are naturally occurring ice-like combinations of gas and water, have the potential to provide vast amounts of natural gas from the world's oceans and polar regions. However, producing gas economically from hydrates entails major technical challenges. Proposed recovery methods such as dissociating or melting gas hydrates by heating or depressurization are currently being tested. One such test was conducted in northern Canada by the partners in the Mallik 2002 Gas Hydrate Production Research Well Program. This paper describes how resistivity logs were used to determine the size of the annular region of gas hydrate dissociation that occurred around the wellbore during the thermal test in the Mallik 5L-38 well. An open-hole logging suite, run prior to the thermal test, included array induction, array laterolog, nuclear magnetic resonance and 1.1-GHz electromagnetic propagation logs. The reservoir saturation tool was run both before and after the thermal test to monitor formation changes. A cased-hole formation resistivity log was run after the test.Baseline resistivity values in each formation layer (Rt) were established from the deep laterolog data. The resistivity in the region of gas hydrate dissociation near the wellbore (Rxo) was determined from electromagnetic propagation and reservoir saturation tool measurements. The radius of hydrate dissociation as a function of depth was then determined by means of iterative forward modeling of cased-hole formation resistivity tool response. The solution was obtained by varying the modeled dissociation radius until the modeled log overlaid the field log. Pretest gas hydrate production computer simulations had predicted that dissociation would take place at a uniform radius over the 13-ft test interval. However, the post-test resistivity modeling showed that this was not the case. The resistivity-derived dissociation radius was greatest near the outlet of the pipe that circulated hot water in the wellbore, where the highest temperatures were recorded. The radius was smallest near the center of the test interval, where a conglomerate section with low values of porosity and permeability inhibited dissociation. The free gas volume calculated from the resistivity-derived dissociation radii yielded a value within 20 per cent of surface gauge measurements. These results show that the inversion of resistivity measurements holds promise for use in future gas hydrate monitoring. ?? 2008 Society of Petrophysicists and Well Log Analysts. All rights reserved.

Conference Paper

Determination of molybenum in soils and rocks: A geochemical semimicro field method

Reconnaissance work in geochemical prospecting requires a simple, rapid, and moderately accurate method for the determination of small amounts of molybdenum in soils and rocks. The useful range of the suggested procedure is from 1 to 32 p.p.m. of molybdenum, but the upper limit can be extended. Duplicate determinations on eight soil samples containing less than 10 p.p.m. of molybdenum agree within 1 p.p.m., and a comparison of field results with those obtained by a conventional laboratory procedure shows that the method is sufficiently accurate for use in geochemical prospecting. The time required for analysis and the quantities of reagents needed have been decreased to provide essentially a "test tube" method for the determination of molybdenum in soils and rocks. With a minimum amount of skill, one analyst can make 30 molybdenum determinations in an 8-hour day.

Analytical Chemistry

Geochemical field method for determination of nickel in plants

The use of biogeochemical data in prospecting for nickel emphasizes the need for a simple, moderately accurate field method for the determination of nickel in plants. In order to follow leads provided by plants of unusual nickel content without loss of time, the plants should be analyzed and the results given to the field geologist promptly. The method reported in this paper was developed to meet this need. Speed is acquired by elimination of the customary drying and controlled ashing; the fresh vegetation is ashed in an open dish over a gasoline stove. The ash is put into solution with hydrochloric acid and the solution buffered. A chromograph is used to make a confined spot with an aliquot of the ash solution on dimethylglyoxime reagent paper. As little as 0.025% nickel in plant ash can be determined. With a simple modification, 0.003% can be detected. Data are given comparing the results obtained by an accepted laboratory procedure. Results by the field method are within 30% of the laboratory values. The field method for nickel in plants meets the requirements of biogeochemical prospecting with respect to accuracy, simplicity, speed, and ease of performance in the field. With experience, an analyst can make 30 determinations in an 8-hour work day in the field.

Analytical Chemistry

Economic decision making and the application of nonparametric prediction models

Sustained increases in energy prices have focused attention on gas resources in low permeability shale or in coals that were previously considered economically marginal. Daily well deliverability is often relatively small, although the estimates of the total volumes of recoverable resources in these settings are large. Planning and development decisions for extraction of such resources must be area-wide because profitable extraction requires optimization of scale economies to minimize costs and reduce risk. For an individual firm the decision to enter such plays depends on reconnaissance level estimates of regional recoverable resources and on cost estimates to develop untested areas. This paper shows how simple nonparametric local regression models, used to predict technically recoverable resources at untested sites, can be combined with economic models to compute regional scale cost functions. The context of the worked example is the Devonian Antrim shale gas play, Michigan Basin. One finding relates to selection of the resource prediction model to be used with economic models. Models which can best predict aggregate volume over larger areas (many hundreds of sites) may lose granularity in the distribution of predicted volumes at individual sites. This loss of detail affects the representation of economic cost functions and may affect economic decisions. Second, because some analysts consider unconventional resources to be ubiquitous, the selection and order of specific drilling sites may, in practice, be determined by extraneous factors. The paper also shows that when these simple prediction models are used to strategically order drilling prospects, the gain in gas volume over volumes associated with simple random site selection amounts to 15 to 20 percent. It also discusses why the observed benefit of updating predictions from results of new drilling, as opposed to following static predictions, is somewhat smaller. Copyright 2007, Society of Petroleum Engineers.

Conference Paper