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Los procedimientos de Métodos Estándares para el Examen de Agua y Residuos se destinados al análisis de una amplia gama de aguas, incluidas las aguas superficiales, las aguas subterráneas, agua salina, agua doméstica e industrial, agua de refrigeración o de circulación, agua de caldera, agua de alimentación de calderas y tratados y no tratados aguas residuales municipales e industriales.

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The procedures described in Standard Methods for the Exam- Methods for analyzing bulk water-treatment chemicals are not

ination of Water and Wastewater are intended for use in analyz- included. American Water Works Association committees pre-

ing a wide range of waters, including surface water, ground pare and issue standards for water treatment chemicals.

water, saline water, domestic and industrial water supplies, cool- Laboratories that desire to produce analytical results of known

ing or circulating water, boiler water, boiler feed water, and quality (i.e., results are demonstrated to be accurate within a

treated and untreated municipal and industrial wastewaters. In specified degree of uncertainty) should use established quality

recognition of the unity of the water, wastewater, and watershed control (QC) procedures consistently. Part 1000 provides a de-

management fields, the analytical methods are categorized based tailed overview of QC procedures used in the individual standard

on constituent, not type of water. methods as prescribed throughout Standard Methods. Other sec-

An effort has been made to present methods that apply gen- tions of Part 1000 address laboratory safety, sampling proce-

erally. When alternative methods are necessary for samples of

dures, and method development and validation. Material pre-

different composition, the basis for selecting the most appropri-

sented in Part 1000 is not necessarily intended to be prescriptive

ate method is presented as clearly as possible. In specific in-

nor to replace or supersede specific QC requirements given in

stances (e.g., samples with extreme concentrations or otherwise

unusual compositions or characteristics), analysts may have to individual sections of this book. Parts 2000 through 9000 contain

modify a method for it to be suitable. If so, they should plainly sections describing QC practices specific to the methods in the

state the nature of the modification when reporting the results. respective Parts; these practices are considered to be integral to

Certain procedures are intended for use with sludges and the methods. Most individual methods will contain explicit in-

sediments. Here again, the effort has been made to present structions to be followed for that method (either in general or for

methods with the widest possible application. However, these certain regulatory applications).

methods may require modification or be inappropriate for chem- Similarly, the overview of topics covered in Part 1000 is not

ical sludges or slurries, or other samples with highly unusual intended to replace or be the sole basis for technical education

composition. and training of analysts. Rather, the discussions are intended as

Most of the methods included here have been endorsed by aids to augment and facilitate reliable use of the test procedures

regulators. Regulators may not accept procedures that were herein. Each Section in Part 1000 contains references that can be

modified without formal approval. reviewed to gain more depth or details for topics of interest.

1010 B. Statistics

repeated measurements (10, 20, 30, etc.):

If a measurement is repeated many times under essentially

identical conditions, the results of each measurement (x) will be x x i/n for estimated mean

distributed randomly about a mean value (arithmetic average)

because of uncontrollable or experimental uncertainty. If an The standard deviation of the entire population measured is as

infinite number of such measurements were accumulated, then follows:

the individual values would be distributed in a curve similar to

those shown in Figure 1010:1. Figure 1010:1A illustrates the

x i 2/n 1/2

Gaussian (normal) distribution, which is described precisely by

the mean () and the standard deviation (). The mean (average)

is simply the sum of all values (xi) divided by the number of The empirical estimate of the sample standard deviation (s) is

values (n). as follows:

Because no measurements are repeated infinitely, it is only The standard deviation fixes the width (spread) of the

possible to make an estimate of the mean (x ) using the same normal distribution and consists of a fixed fraction of the

1

INTRODUCTION (1010)/Statistics

Figure 1010:1. Three types of frequency distribution curvesnormal Gaussian (A), positively skewed (B), and negatively skewed

(C)and their measures of central tendency: mean, median, and mode. Courtesy: L. Malcolm Baker.

measurements that produce the curve. For example, 68.27% where t has the following values for 95% confidence intervals:

of the measurements lie within 1, 95.45% between

within 2, and 99.73% within 3. (It is sufficiently

n t n t

accurate to state that 95% of the values are within 2 and

99% within 3.) When values are assigned to the 2 12.71 5 2.78

multiples, they are called confidence limits, and the range 3 4.30 10 2.26

between them is called the confidence interval. For example, 4 3.18 1.96

10 4 indicates that the confidence limits are 6 and 14, and

the confidence interval ranges from 6 to 14. Using t compensates for the tendency of a small number of

Another useful statistic is the standard error of the mean values to underestimate uncertainty. For n 15, it is common to

()the standard deviation divided by the square root of the use t 2 to estimate the 95% confidence interval.

number of values / n). This is an estimate of sampling accu- Still another statistic is the relative standard deviation (/)

racy; it implies that the mean of another sample from the same with its estimate (s/x), also known as the coefficient of variation

population would have a mean within some multiple of . As (CV), which commonly is expressed as a percentage. This sta-

with , 68.27% of the measurements lie within 1, tistic normalizes and sometimes facilitates direct comparisons

95.45% within 2, and 99.73% within 3. In among analyses involving a wide range of concentrations. For

practice, a relatively small number of average values is available, example, if analyses at low concentrations yield a result of 10

so the confidence intervals about the mean are expressed as: 1.5 mg/L and at high concentrations yield a result of 100 8

mg/L, the standard deviations do not appear comparable. How-

x ts/ n ever, the percent relative standard deviations are 100 (1.5/10)

2

INTRODUCTION (1010)/Statistics

15% and 100 (8/100) 8%, indicating that the variability is not TABLE 1010:I. CRITICAL VALUES FOR 5% AND 1% TESTS OF

as great as it first appears. DISCORDANCY FOR A SINGLE OUTLIER IN A NORMAL SAMPLE

The mean, median, and mode for each curve in Figure 1010:1 Number of

were calculated as follows: Critical Value

Measurements

1) Mean is the value at the 50th percentile level, or arithmetic n 5% 1%

average,

2) Mode is the value that appears most frequently, and 3 1.15 1.15

3) Median1 is estimated as follows: 4 1.46 1.49

5 1.67 1.75

6 1.82 1.94

Median 13 2 Mean Mode) 7 1.94 2.10

8 2.03 2.22

2. Log-Normal Distribution 9 2.11 2.32

10 2.18 2.41

In many cases, the results obtained from analyzing environ- 12 2.29 2.55

mental samples will not be normally distributed [i.e., a graph of 14 2.37 2.66

15 2.41 2.71

the data distribution will be obviously skewed (see Figure

16 2.44 2.75

1010:1B and C)] so the mode, median, and mean will be dis- 18 2.50 2.82

tinctly different. To obtain a nearly normal distribution, convert 20 2.56 2.88

the measured variable results to logarithms and then calculate x 30 2.74 3.10

and s. The antilogarithms of x and s are the estimates of geo- 40 2.87 3.24

metric mean (x g) and geometric standard deviation (sg). The 50 2.96 3.34

geometric mean is defined as: 60 3.03 3.41

100 3.21 3.60

x g x i 1/n antilog 1/n log xi 120 3.27 3.66

SOURCE: BARNET, V. & T. LEWIS. 1995. Outliers in Statistical Data, 3rd ed. John

3. Least Square Curve Fitting Wiley & Sons, New York, N.Y.

quadratic curve by the least squares method, which is used to

determine the constants of the curve that the data points best fit. a more detailed description of the algebraic manipulations, see

To do this, choose the equation that best fits the data points and the cited references.

assume that x is the independent variable and y is the dependent In this case, the correlation coefficient1 is:

variable (i.e., use x to predict the value of y). The sum of the

squares of the differences between each actual data point and its y2 a0 y a1 xy a2 x2 y 0.5

predicted value are minimized. r 1

1

For a linear least squares fit of y2 y2

n

y mx b 4. Rejecting Data

the slope (a1) and the y intercept13 (a0) are computed as follows: In a series of measurements, one or more results may differ

greatly from the others. Theoretically, no result should be arbi-

xy/n xy

m trarily rejected because it may indicate either a faulty technique

x 2/n x 2 (casting doubt on all results) or a true variant in the distribution.

y mx In practice, it is permissible to reject the result of any analysis in

b which a known error occurred. In environmental studies, ex-

n

tremely high and low concentrations of contaminants may indi-

The correlation coefficient13 (degree of fit) is: cate either problematic or uncontaminated areas, so they should

not be rejected arbitrarily.

rm xy/n xy

y 2 y 2/n

0.5 An objective test for outliers has been described.4 If a set of

data is ordered from low to high (xL, x2 . . . xH) and the mean and

standard deviation are calculated, then suspected high or low

The best fit is when r 1. There is no fit when r 0. outliers can be tested via the following procedure. First, calculate

For a quadratic least squares fit of the statistic T using the discordancy test for outliers:

the constants (a0, a1, and a2)13 must be calculated. Typically, T (x x L )/s for a low value.

these calculations are performed using software provided by

instrument manufacturers or independent software vendors. For Second, compare T with the value in Table 1010:I for either a

3

INTRODUCTION (1010)/Glossary

5% or 1% level of significance for the number of measurements 3. TEXAS INSTRUMENTS, INC. 1975. Texas Instruments Programmable

(n). If T is larger than that value, then xH or xL is an outlier. Calculator Program Manual ST1. Statistics Library, Dallas, Texas.

Further information on statistical techniques is available else- 4. BARNETT, V. & T. LEWIS. 1995. Outliers in Statistical Data, 3rd ed.,

where.57 John Wiley & Sons, New York, N.Y.

5. NATRELLA, M.G. 1963. Experimental Statistics, Handbook 91. Na-

tional Bur. Standards, Washington, D.C.

5. References 6. SNEDECOR, G.W. & W.G. COCHRAN. 1980. Statistical Methods. Iowa

State University Press, Ames.

1. SPIEGEL, M.R. & L.J. STEPHENS. 1998 Schaums OutlineTheory and 7. VERMA, S.P. & A. QUIROZ-RUIZ. 2006. Critical values for 22 discor-

Problems of Statistics. McGraw-Hill, New York, N.Y. dancy test variants for outliers in normal samples up to sizes 100, and

2. LAFARA, R.L. 1973. Computer Methods for Science and Engineering. applications in science and engineering. Revista Mexicana de Cien-

Hayden Book Co., Rochelle Park, N.J. cias Geologicas 23(3):302.

1010 C. Glossary

This glossary defines concepts, not regulatory terms. It is not preferred level of acceptable reliability. Examples of

intended to be all-inclusive. RLs typically used (besides the MDL) include:

Accuracy estimate of how close a measured value is to the true Level of quantitation (LOQ)/minimum quantifiable level

value; includes expressions for bias and precision. (MQL)the analyte concentration that produces a signal

Analytethe element, compound, or component being analyzed. sufficiently stronger than the blank, such that it can be

Bias consistent deviation of measured values from the true detected with a specified level of reliability during

value, caused by systematic errors in a procedure. routine operations. Typically, it is the concentration

Calibration check standardstandard used to determine an that produces a signal 10s above the reagent water

instruments accuracy between recalibrations. blank signal, and should have a defined precision and

Confidence coefficientthe probability (%) that a measurement bias at that level.

will lie within the confidence interval (between the confidence Minimum reporting level (MRL)the minimum concen-

limits). tration that can be reported as a quantified value for a

Confidence intervalset of possible values within which the target analyte in a sample. This defined concentration

true value will lie with a specified level of probability. is no lower than the concentration of the lowest cali-

Confidence limitone of the boundary values defining the bration standard for that analyte and can only be used

confidence interval. if acceptable QC criteria for this standard are met.

Detection levelsvarious levels in use are: Duplicate1) the smallest number of replicates (two), or 2)

Instrument detection level (IDL)the constituent concentration duplicate samples (i.e., two samples taken at the same time

that produces a signal greater than five times the instruments from one location) (field duplicate) or replicate of laboratory

signal:noise ratio. The IDL is similar to the critical level and analyzed sample.

criterion of detection, which is 1.645 times the s of blank Fortificationadding a known quantity of analyte to a sample or

analyses (where s is the estimate of standard deviation). blank to increase the analyte concentration, usually for the

Lower level of detection (LLD) [also called detection level and purpose of comparing to test result on the unfortified sample

level of detection (LOD)]the constituent concentration in and estimating percent recovery or matrix effects on the test to

reagent water that produces a signal 2(1.645)s above the mean assess accuracy.

of blank analyses. This establishes both Type I and Type II Internal standarda pure compound added to a sample extract

errors at 5%. just before instrumental analysis to permit correction for in

Method detection level (MDL)the constituent concentration efficiencies.

that, when processed through the entire method, produces a Laboratory control standarda standard usually certified by an

signal that has 99% probability of being different from the outside agency that is used to measure the bias in a procedure.

blank. For seven replicates of the sample, the mean must be For certain constituents and matrices, use National Institute of

3.14s above the blank result (where s is the standard deviation Standards and Technology (NIST) or other national or inter-

of the seven replicates). Compute MDL from replicate national traceable sources (Standard Reference Materials),

measurements of samples spiked with analyte at concen- when available.

trations more than one to five times the estimated MDL. Meanthe arithmetic average (the sum of measurements divided

The MDL will be larger than the LLD because typically by the number of items being summed) of a data set.

7 or less replicates are used. Additionally, the MDL will Medianthe middle value (odd count) or mean of the two middle

vary with matrix. values (even count) of a data set.

Reporting level (RL)the lowest quantified level within an Modethe most frequent value in a data set.

analytical methods operational range deemed reliable Percentilea value between 1 and 100 that indicates what percent-

enough, and therefore appropriate, for reporting by the age of the data set is below the expressed value.

laboratory. RLs may be established by regulatory mandate Precision (usually expressed as standard deviation)a measure of

or client specifications, or arbitrarily chosen based on a the degree of agreement among replicate analyses of a sample.

4

INTRODUCTION (1010)/Dilution/Concentration Operations

Quality assessmentprocedure for determining the quality of Rangethe difference of the largest and smallest values in a data

laboratory measurements via data from internal and external set.

quality control measures. Replicaterepeated operation during an analytical procedure.

Quality assurancea definitive plan for laboratory operations that Two or more analyses for the same constituent in an extract of

specifies the measures used to produce data with known precision one sample constitute replicate extract analyses.

and bias. Spikesee fortification.

Quality controlset of measures used during an analytical Surrogate standarda pure compound added to a sample in the

method to ensure that the process is within specified control laboratory just before processing so a methods overall effi-

parameters. ciency can be determined.

Random errorthe deviation in any step in an analytical Type I error (also called alpha error)the probability of deter-

procedure that can be treated by standard statistical tech- mining that a constituent is present when it actually is absent.

niques. Random error is a major component of measure- Type II error (also called beta error)the probability of not

ment error and uncertainty. detecting a constituent that actually is present.

1. Adjusting Solution Volume total volume will equal a b, which is not always the case).

Most aqueous-solution volumes are additive, but alcoholic solu-

Analysts frequently must dilute or concentrate the amount of tions or concentrated acid may be only partially volumetrically

analyte in a standard or sample aliquot to within a range suitable additive, so be aware of potential problems when combining

for the analytical method so analysis can be performed with nonaqueous solutions with aqueous diluents.

specified accuracy. The following equations enable analysts to b. Volumetric dilution to a measured volume (a/c). This

compute the concentration of a diluted or concentrated aliquot method is used to dilute an aliquot to a given volume via a pipet

based on the original aliquot concentration and an appropriate and volumetric flask. It is the most accurate means of dilution,

factor or fractional constant. (A factor in this context is the ratio but when fortifying sample matrices, some error can be intro-

of final adjusted volume to original volume.) They also can duced if a regular Class A volumetric flask is used. The error will

compute the concentration of adjusted aliquot volume based on be proportional to the volumes of both spiking solution and flask.

the original aliquot volume. For the most accurate work, measure the unfortified sample

aliquot in a 100-mL Cassia Class A volumetric flask to the

Concentration of diluted aliquot 100-mL mark (0.0 on the flask neck*), and then pipet the volume

original aliquot concentration dilution fraction of fortifying solution. Mix the solution and note the graduated

volume on the neck of the flask. The fortified solutions true

Concentration of original aliquot volume is equal to 100 mL graduated volume over 100 mL.

The true total volume is necessary when computing the dilution

diluted aliquot concentration dilution factor

factor for the percent recovery of fortified analyte (LFM) in

Concentration of concentrated aliquot Sections 1020B.12e and 4020B.3a to obtain the most accurate

analytical estimate of recovery.

original aliquot concentration concentration factor Dilution factors for multiple volumetric dilutions are calcu-

Concentration of original aliquot lated as the product of the individual dilutions. Generally, serial

dilution is preferred when making dilutions of more than two or

concentrated aliquot concentration concentration fraction three orders of magnitude. Avoid trying to pipet quantities of less

than 1.0 mL into large volumes (e.g., 1.0 mL into 100 or 1000

where: mL) to avoid large relative error propagation.

Dilution fraction original volume/adjusted volume, Some biological test methods (e.g., BOD or toxicity testing) may

Dilution factor adjusted volume/original volume, include dilution techniques that do not strictly conform to the pre-

Concentration factor original volume/adjusted volume, and ceding descriptions. For example, such techniques may use

Concentration fraction adjusted volume/original volume. continuous-flow dilutors and dilutions prepared directly in test

equipment, where volumes are not necessarily prepared via Class A

2. Types of Dilutions volumetric equipment. Follow the method-specific dilution directions.

3. Bibliography

Several types of dilutions are used in Standard Methods pro-

cedures. Two of the most common volumetric techniques critical

NIEMELA, S.I. 2003. Uncertainty of Quantitative Determinations Derived

to analytical chemistry results are:

by Cultivation of Microorganisms, Publication J4/2003 MIKES.

a. Volumetric addition [a/(a b)]. This method typically is Metrologia, Helsinki, Finland.

used to dilute microbiological samples and prepare reagents

from concentrated reagents. It assumes that volumes a and b are

additive (i.e., when a is combined with b in one container, the * Pyrex, or equivalent.

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