Pnd f definition of np in water. The problem of the presence of oil products in water and how to deal with it. List of normative and methodological documents PND F in force on the territory of the Russian Federation

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FEDERAL SUPERVISION SERVICE
IN THE SPHERE OF NATURE MANAGEMENT

QUANTITATIVE CHEMICAL ANALYSIS OF WATER

MEASUREMENT TECHNIQUE
MASS CONCENTRATION OF PETROLEUM PRODUCTS
IN DRINKING, NATURAL AND TREATED WASTE
WATER BY IR SPECTROPHOTOMETRY
USING KH SERIES CONCENTRATOMETER

PND F 14.1:2:4.168-2000

(FR.1.31.2010.07432)

(Edition 2012)

The technique is approved for purposes
state environmental control

MOSCOW 2012

The methodology was reviewed and approved by the federal budgetary institution " federal center Analysis and Assessment of Technogenic Impact” (FBU “FTsAO”).

This edition of the methodology is valid until the release of a new edition.

Developers:

LLC "Industrial and ecological enterprise "SIBEKOPRIBOR"

federal state state-financed organization science institute organic chemistry them. N.N. Vorozhtsov of the Siberian Branch of the Russian Academy of Sciences (NIOC SB RAS)

1 PURPOSE AND SCOPE

This document specifies the measurement procedure mass concentration petroleum products (hereinafter - NP) in drinking, natural and purified Wastewater ah by IR spectrophotometry using KN series concentrators.

Measurement range from 0.02 to 2 mg/dm 3 .

The interfering influence of other substances present in the water sample is eliminated during the sample preparation process.

2 REGULATORY REFERENCES

Weight for calibration with a nominal value of mass 200 g E 2 according to GOST 7328

Pipettes with a capacity of 5, 10 cm 3 in accordance with GOST 29227

Volumetric flasks with a capacity of 50 cm 3 according to GOST 1770

Measuring cylinders with a capacity of 10, 25, 1000 cm 3 according to GOST 1770

4.2 Reference materials

State standard sample of the composition of a solution of petroleum products (hydrocarbons) in carbon tetrachloride GSO 7822-2000, GSO 7248-96

State standard sample of the composition of petroleum products in a water-soluble matrix GSO 7117-94

4.3 Accessories

Drying cabinet for general laboratory, providing temperature maintenance from 105 to 110 °С

Muffle furnace PM-8 according to TU 79-337

Laboratory extractor EL-1 ISHVZh.002 PS

Dividing funnels with a capacity of 0.5; 1.0 dm 3 according to GOST 25336

Electric stove with a closed spiral in accordance with GOST 14919

Solvent distillation glass plant:

Distillation flask with a capacity of 1 dm 3 according to GOST 25336;

Christmas tree dephlegmator (at least 25 cm long) in accordance with GOST 25336;

Refrigerator HPT (at least 30 cm long) in accordance with GOST 25336;

Laboratory thermometer (from 0 to 100 °С, division value 0.1 °С) in accordance with GOST 28498

Flat-bottom conical flask according to GOST 25336

Weighing cup (bux) high in accordance with GOST 25336

Chromatographic column - glass tube with inner diameter 7 mm, length 200 mm

Stand for chromatographic columns

Sieve with a hole diameter of 0.16 mm

Desiccator with silica gel or dehydrated calcium chloride according to GOST 25336

Conical flasks with ground stopper in accordance with GOST 25336

Glass rods (12 - 15) cm long

Glass bottles with a capacity of 1.0 dm 3 for sampling and storage of samples

4.4 Reagents and materials

Carbon tetrachloride, chemically pure according to GOST 20288 or for extraction from aqueous media, chemically pure. according to TU 2631-027-44493179

Aluminum oxide for chromatography according to TU 6-09-3916 or analytical grade. according to GOST 8136

Sodium sulfate anhydrous, hours in accordance with GOST 4166

Fiberglass or glass wool according to GOST 10727

Universal indicator paper for determining pH according to TU 6-09-1181

Note- It is allowed to use other equipment, materials and reagents with metrological and technical specifications similar to those indicated.

5 MEASUREMENT METHOD

Measurement of the mass concentration of NPs in drinking, natural and treated wastewater is performed by IR spectrum photometric method.

The method for measuring the mass concentration of NPs is based on the dependence of the absorption intensity S-H ties in the infrared region of the spectrum (2930 ± 70) cm -1 on the mass concentration of NP in the eluate.

The analysis procedure consists in the extraction of emulsified and dissolved oil components from water by extraction with carbon tetrachloride, chromatographic separation of petroleum products from related organic compounds of other classes on a column filled with aluminum oxide.

6 SAFETY AND ENVIRONMENTAL REQUIREMENTS

6.1 When performing measurements, it is necessary to comply with safety requirements when working with chemical reagents in accordance with GOST 12.1.007.

6.2 Electrical safety when working with electrical installations is observed in accordance with GOST 12.1.019.

6.3 The laboratory premises must comply with the requirements fire safety in accordance with GOST 12.1.004 and have fire extinguishing equipment in accordance with GOST 12.4.009. Content harmful substances should not exceed the permissible concentrations in accordance with GOST 12.1.005.

6.4 The organization of training of workers in labor safety is carried out in accordance with GOST 12.0.004.

7 OPERATOR QUALIFICATION REQUIREMENTS

Persons with the qualification of a chemical engineer or chemical technician who have experience in a chemical laboratory, who have received appropriate instruction, who have mastered the method in the process of training and have received satisfactory results of control measurements, are allowed to perform measurements and process their results.

8 REQUIREMENTS FOR MEASUREMENT CONDITIONS

When performing measurements, the following conditions are observed:

Ambient temperature, °С (20 ± 5);

Atmospheric pressure, kPa (mm Hg) (84.0 - 106.7) (630 - 800);

Relative air humidity (at t = 25 °С), %, no more than 80;

AC frequency, Hz (50 ± 1);

Power supply voltage, V (220 ± 22);

The environment is non-explosive.

9 PREPARATION FOR MEASUREMENTS

9.1 Sampling

9.1.1 Water sampling is carried out in accordance with the requirements of GOST R 51592, GOST R 51593, GOST 17.1.4.01.

When sampling, the capture of the NP film from the surface of the water should be excluded. The selected samples are placed in glass bottles, used completely and not filtered.

The volume of the sample taken, depending on the expected content of NPs in the water, must correspond to the values \u200b\u200bspecified in Table 2.

Table 2 - The volume of water samples depending on the expected content of OP

9.1.2 Extraction of OP from water is carried out no later than 3 hours after sampling.

9.1.3 If it is impossible to carry out extraction during this period, the sample is preserved by adding a mixture of sulfuric acid and carbon tetrachloride at the rate of 1 cm 3 of concentrated acid and (2.0 - 3.0) cm 3 of carbon tetrachloride per 1 dm 3 of the sample. When extracting these volumes should be taken into account. Preservatives may be added to the empty container prior to sampling. The shelf life of canned water samples is 1 month from the date of sampling.

9.1.4 When sampling, an accompanying document is drawn up in the approved form, which indicates:

Purpose of analysis, suspected contaminants;

Place, time of selection;

Sample number;

Position, name of the specialist taking the sample, date.

9.2 Preparation of glassware, reagents and materials

9.2.1 Preparing glassware and measuring cell

When performing measurements of the mass concentration of NPs, it is necessary to carefully observe the cleanliness of chemical glassware.

For washing chemical dishes it is allowed to use concentrated sulfuric and nitric acids. Do not use all types of synthetic detergents for washing.

Rinse the cuvette for at least three times carbon tetrachloride prepared according to 9.2.2.

Thoroughly wash the utensils intended for preparing solutions, collecting the extract and eluate, rinsing at least twice with distilled water, drying and then rinsing with carbon tetrachloride prepared according to 9.2.2, with a volume sufficient to fill the measuring cuvette. To control the cleanliness of these dishes, carbon tetrachloride collected after rinsing is poured into a cuvette and the mass concentration of NP is measured in accordance with 10.3. If the measured value of the mass concentration of OP does not exceed 0.6 mg/dm3, then the glassware and cuvette are suitable for work. If the specified value is exceeded, the preparation of dishes and cuvettes must be repeated.

9.2.2 Preparation of carbon tetrachloride

Check the purity of each batch of carbon tetrachloride in accordance with the instruction manual for the concentrator used. If the reading does not exceed 20.0 mg / dm 3, then carbon tetrachloride is suitable for work. Otherwise, carry out the purification of carbon tetrachloride as follows.

In a separating funnel of the extractor EL-1 with a capacity of 1 dm 3, 0.4 dm 3 of carbon tetrachloride is placed, 0.5 dm 3 of distilled water is added and stirred for 1 minute. A layer of carbon tetrachloride is poured into the flask. The procedure is repeated with new portion distilled water.

About 10 g of anhydrous sodium sulfate is added to the washed carbon tetrachloride and, stirring occasionally, is kept for (10 - 15) minutes. Dehydrated carbon tetrachloride is decanted into a distillation flask and distilled at a temperature range from 76 to 78 ° C, collecting separately the first (50 - 60) cm 3 (then discarded), the main fraction (actually purified carbon tetrachloride) and leaving about 50 cm3 in the distillation flask 3 carbon tetrachloride.

When carrying out the purification of carbon tetrachloride in the extractor EL-1, they are guided by the passport for EL-1.

In the absence of the EL-1 extractor, it is allowed to carry out cleaning in a separating funnel by shaking.

9.2.3 Preparation of grade 2 alumina

Alumina is sifted through a sieve with a hole diameter of 0.16 mm and a fraction (0.16 - 0.25) mm is used. Then the alumina is washed with carbon tetrachloride, prepared according to 9.2.2, so that carbon tetrachloride covers the layer of alumina, then it is dried in air in a fume hood, calcined in a porcelain or quartz cup in muffle furnace at a temperature of (550 - 600) ° C for 4 hours, cooled to (100 - 200) ° C in an oven, then placed in a desiccator and cooled to room temperature.

If, upon calcination, aluminum oxide acquires yellow then it is unusable. The shelf life of calcined aluminum oxide in a tightly closed container is 1 month.

Before use, the required amount of calcined aluminum oxide is weighed, distilled water is added so that the mass of distilled water is 3% of the mass of aluminum oxide, tightly closed, shaken for several minutes and kept for a day at room temperature.

9.2.4 Preparation of anhydrous sodium sulfate

Before use, anhydrous sodium sulfate is dried at a temperature of (105 - 110) ° C for 8 hours in an oven, cooled and stored in a desiccator. The shelf life is 1 month.

9.2.5 Preparation of sodium chloride

Sodium chloride is calcined in a porcelain or quartz cup in a muffle furnace at a temperature of (550 - 600) ° C, then cooled. Calcined sodium chloride is stored in a desiccator or in a flask with a ground stopper. The shelf life is 1 month.

9.2.6 Preparation of sulfuric acid solution 1:9

In a heat-resistant container, 9 volumes of distilled water and 1 volume of concentrated sulfuric acid are mixed. The acid is carefully added to the water.

9.2.7 Preparation of glass fibers or glass wool

Glass fiber or glass wool is kept in dilute (1:1) sulfuric or nitric acid for 12 hours, washed with tap water, then with distilled water and dried in an oven. Before use, glass fibers or glass wool are thoroughly washed with carbon tetrachloride and dried at room temperature.

Note- It is allowed to use medical cotton wool according to GOST 5556 (cotton, not synthetic!). Before use, cotton wool is thoroughly washed with carbon tetrachloride and dried at room temperature.

9.2.8 Preparing the chromatographic column

A layer (~ 0.5 cm) of glass fiber or glass wool, prepared according to 9.2.7, is placed in the lower (drawn) part of the column. Then, 3 g of alumina prepared according to 9.2.3 is poured into the chromatographic column, and the glass fiber or glass wool layer is again placed. Pass through the column 10 cm 3 of carbon tetrachloride. The first portion of carbon tetrachloride passed through the column - eluate (~ 3 cm 3) is discarded. The next portion of the eluate is collected in a clean beaker. The measuring cuvette is preliminarily rinsed with a small amount of eluate, then it is filled and the mass concentration of OP in the eluate is measured in accordance with 10.3. If the measured value of the mass concentration of OP in the eluate does not exceed 0.6 mg/dm 3 , then the chromatographic column is suitable for work. If the specified value is exceeded, the chromatographic column is washed with new portions of carbon tetrachloride.

Aluminum oxide is used in the chromatographic column once.

9.2.9 Carbon tetrachloride recovery

Plums of carbon tetrachloride formed in the process of preparing the device for operation, rinsing the dishes during preparation and during the determination, as well as after analyzing the samples, are collected in a bottle for draining 2) .

2) Plums of carbon tetrachloride containing GSO NP (hydrocarbons), not subject to distillation!

When a sufficient amount of drains has accumulated, the solvent is cleaned using one of the following methods:

In accordance with MI "PEP "SIBEKOPRIBOR" No. 06-02 "Guidelines for the adsorption treatment of waste carbon tetrachloride";

After drying with sodium sulfate, it is distilled, collecting the middle fraction.

Check the purity of the resulting carbon tetrachloride according to 9.2.2 and, if necessary, repeat the purification.

If in this way it is not possible to achieve the desired degree of purification of carbon tetrachloride, it is not suitable for further use.

9.2.10 Preparation of purified distilled water

A water sample is extracted at the rate of 20 cm 3 of carbon tetrachloride per 1 dm 3 of water.

9.3 Preparation of solutions

9.3.1 Preparation of the main solution of NP mass concentration of 1000 mg / dm 3

The main solution is prepared from the GSO 7822-2000 composition of the solution of NP (hydrocarbons) in carbon tetrachloride 3) as follows.

3) It is allowed to use the GSO of the composition of the solution of NP (hydrocarbons) in carbon tetrachloride of another type (for example, GSO 7248-96) with similar metrological characteristics. In this case, the preparation of the stock solution should be carried out in accordance with the instructions for use of this GSO.

The ampoule is opened, the solution from the ampoule is carefully transferred without loss into a volumetric flask with a capacity of 50 cm 3 through a funnel. Then the ampoule is thoroughly washed 5 times with carbon tetrachloride in portions of 3 cm 3, poured into a volumetric flask, thoroughly washing the surface of the funnel, the volume of the solution is adjusted to the mark with carbon tetrachloride and mixed. The solution can be stored in a refrigerator at a temperature of (0 - 5) ° C for no more than 6 months. Before use, the solution is kept at room temperature for at least 30 minutes.

The main solution is prepared again in case of a change in the batch of carbon tetrachloride.

9.3.2 Preparation of a working solution of NP mass concentration of 100 mg / dm 3

The working solution of NP in carbon tetrachloride is prepared by diluting the stock solution of NP. To do this, pipette 5.0 cm 3 of the main solution of NP into a volumetric flask with a capacity of 50 cm 3, bring the volume of the solution in the flask to the mark with carbon tetrachloride and mix.

The solution can be stored in a refrigerator at a temperature of (0 - 5) ° C for no more than 2 months. Before use, the solution is kept at room temperature for at least 30 minutes.

The mass concentration of NP in the resulting solution is 100 mg/DM 3 .

The working solution is used to set the initial values (calibration) in accordance with 9.4.

9.3.3 Preparation of NP calibration solutions

Calibration solutions are prepared immediately before use by diluting the working solution. To do this, in volumetric flasks with a capacity of 50 cm 3 make a pipette sequentially 1.0; 2.5; 5.0; 10.0 cm 3 of the working solution and bring the volumes of solutions in flasks to the mark with carbon tetrachloride. The solutions are thoroughly mixed. The mass concentration of the resulting solutions is 2, 5, 10, 20 mg/DM 3 respectively.

The relative error in the preparation of solutions does not exceed 2%.

Calibration solutions are used to control the efficiency of the concentrator in the range of measured values of mass concentrations of OP.

9.3.4 Checking the stability of the calibration characteristic

Control of the stability of the calibration characteristics is carried out at least once a quarter or when changing batches of reagents.

The means of control are newly prepared samples for calibration (at least 2 samples from those given in 9.3.3). For each sample, at least two measurements of the mass concentration of OP in calibration solutions are carried out. The first measurement result is not taken into account.

The calibration characteristic is considered stable if the following condition is met for each sample for calibration:

|Xi - C| £ ∆ C AND, (1)

where X i is the result control measurement mass concentration of NP in the calibration sample, mg/dm 3 ;

C - certified value of the mass concentration of NP in the sample for calibration, mg/dm 3 ;

Δ c and - the limit of the permissible basic absolute measurement error in accordance with the instruction manual for the device, mg / dm 3, calculated by the formula

Δ Cu = 0.50 + 0.05 × C. (2)

If the stability condition for the calibration characteristic is not met for only one calibration sample, it is necessary to re-measure this sample to eliminate the result containing a gross error.

If the calibration characteristic is unstable, find out and eliminate the causes and repeat the control using other samples provided by the procedure.

9.4 Preparing and using the concentrator

Preparation for operation, setting the initial values and monitoring the performance of the KN series concentrator is carried out in accordance with the operating manual.

To set the initial values (calibration), pure carbon tetrachloride and a working solution of NP with a mass concentration of 100 mg/dm 3 are used, prepared from carbon tetrachloride used in the analysis.

10 MAKING MEASUREMENTS

10.1 Extraction

The sample of the analyzed water is completely transferred into a separating funnel of the appropriate capacity, sulfuric acid diluted (1:9) to pH ~ 2 is added (control by indicator paper).

If the water sample has been pre-preserved in accordance with 9.1.4, do not add sulfuric acid.

Then add 40 g of sodium chloride, prepared according to 9.2.5, per 1 dm 3 of the water sample. The container in which the sample was located is thoroughly rinsed with 5 cm 3 of carbon tetrachloride and the solvent is poured into a separating funnel. Another 5 cm 3 of carbon tetrachloride are added there (taking into account conservation, the total volume of carbon tetrachloride in the separating funnel should be 10 cm 3).

After phase separation, the lower layer (extract) is poured into a conical flask with a ground stopper and subjected to the treatment according to 10.2 or left for storage. (The shelf life of extracts should not exceed 10 months). After separation of the extract, the volume of the analyzed water sample is measured with a graduated cylinder.

When carrying out extraction using the EL-1 extractor, they are guided by the passport. In the absence of the EL-1 extractor, it is allowed to carry out extraction in a separating funnel by shaking the water sample for 10 minutes.

10.2 Extract processing

The extract is dried with anhydrous sodium sulfate for 10 minutes (based on at least 2 g of sodium sulfate per 10 cm 3 of the extract), adding it to the glass in small portions while stirring the contents with a glass rod. After completion of the drying process, the extract is poured into a measuring cylinder with a capacity of (10 - 25) cm 3 .

Pour 3 cm 3 of carbon tetrachloride into a chromatographic column prepared according to 9.2.8 for wetting. As soon as carbon tetrachloride is absorbed into aluminum oxide, the extract is passed through a chromatographic column. Care must be taken that the liquid level does not fall below the top layer of aluminum oxide. The first 3 cm 3 of the eluate are discarded, and the remainder of the eluate is collected in a flask with a ground stopper.

10.3 Taking measurements

Measurements are carried out in accordance with the operating manual of the concentrator. The measuring cuvette prepared according to 9.2.1 is pre-rinsed with a small amount of the eluate obtained according to 10.2 and then filled into the cuvette. Install the cuvette in the device and measure the mass concentration of NP in the eluate, reading the instrument readings.

If the mass concentration of OP exceeds the upper limit of the measurement range of the device, then the eluate is diluted with carbon tetrachloride prepared according to 9.2.2. Then the solution is poured into a cuvette, which is pre-rinsed with this solution, installed in the device and the measurement is made.

Note- The analyzed solution is diluted no more than 20 times. The dilution of the solution is carried out with carbon tetrachloride, which was used in the analysis.

10.4 Determination of NP in a blank

10.4.1 Determination of the mass concentration of NP in a blank sample is performed simultaneously with the analysis of a series of samples. To do this, take 1.0 dm3 of distilled water purified according to 9.2.10 and process it as described in 10.1 - 10.2. Measure the mass concentration of the OP in the eluate in accordance with 10.3.

10.4.2 If the measured value of the mass concentration of OP in the eluate is negative, then it is necessary to purify carbon tetrachloride according to 9.2.2. Then repeat the procedure for preparing solutions in accordance with 9.3 and carry out the setting of initial values (calibration) in accordance with 9.4.

10.4.3 If the measured value of the mass concentration of NP in the blank sample exceeds 0.02 mg/dm 3, then the determination is repeated and, if necessary, the cause of contamination of the blank sample is identified and eliminated.

The analysis of a blank sample is also carried out when using a new batch of reagents.

The results of the analysis of a blank sample are taken into account when calculating the mass concentration of OP in the sample.

11 CALCULATION (PROCESSING) OF MEASUREMENT RESULTS

11.1 Mass concentration of NP X, mg/dm 3 , in a water sample is calculated by the formula

where X meas - the result of measuring the mass concentration of NP in the eluate on the concentrator, mg/DM 3 ;

V eq - the volume of carbon tetrachloride used for extraction (V eq = 10 cm 3);

K is the dilution factor, i.e. the ratio of the volumes of the volumetric flask and the aliquot of the eluate (taken into account when diluting according to 10.3);

V is the volume of the analyzed water sample, cm 3 .

X cold - the result of measuring the mass concentration of NP in a blank sample, mg/DM 3 .

11.2 The result of a single measurement is taken as the result of the analysis of the mass concentration of NP.

12 PRESENTATION OF MEASUREMENT RESULTS

12.1 The measurement result of X in documents providing for its use can be represented as

X ± Δ, P = 0.95, (4)

Δ - an indicator of the accuracy of the technique, mg / dm 3.

The Δ value is calculated by the formula: Δ = 0.01 × δ × X. The δ value is shown in Table 1.

12.2 It is permissible to present the result of measurements in the documents issued by the laboratory in the form

X ± Δ l, P = 0.95 subject to Δ l< Δ, (5)

where X is the measurement result obtained in accordance with the prescription of the methodology, mg / dm 3;

Δ l - the value of the characteristics of the measurement results error, established during the implementation of the methodology in the laboratory and provided by the control of the stability of the measurement results, mg/dm 3 .

Note- It is permissible to establish the characteristic of the error of the measurement results when implementing the methodology in the laboratory on the basis of the expression: Δ l = 0.84 × Δ, with subsequent refinement as information accumulates in the process of monitoring the stability of the measurement results.

13 PROCEDURES TO ENSURE MEASUREMENT RELIABILITY

13.1 Ensuring the reliability of measurements is organized and carried out by checking the acceptability of measurement results obtained under conditions of repeatability, intralaboratory precision, reproducibility, operational control measurement procedures and stability control of measurement results in accordance with GOST R ISO 5725-6.

13.2 Verification of the acceptability of measurement results obtained under repeatability conditions

13.2.1 The verification of the acceptability of the measurement results obtained under repeatability conditions is carried out according to the results of measurements of the mass concentration of NP in the control samples prepared on the basis of standard samples of the composition of the NP solution.

13.2.2 The measurement results are considered acceptable if the condition is met

where X 1 and X 2 - the results of measurements of the mass concentration of OP, obtained in terms of repeatability, mg/DM 3 ;

r- repeatability limit, %. Repeatability limit values are given in Table 3.

Table 3 - Measurement range, values of the repeatability limit at a confidence level P = 0.95

13.2.3 If condition (6) is not met, the experiment is repeated. If condition (6) is repeatedly violated, it is necessary to find out and exclude the causes of unacceptable results of measurements of the mass concentration of OP under repeatability conditions.

13.3 Verification of the acceptability of measurement results obtained under conditions of intralaboratory precision

13.3.1 The verification of the acceptability of the measurement results obtained under conditions of intralaboratory precision is carried out on the basis of the results of measurements of the mass concentration of NPs in control samples prepared on the basis of standard samples of the composition of the NP solution.

13.3.2 Difference between single measurement results obtained in one laboratory in different conditions, should not exceed the limit of intralaboratory precision

where X 1 and X 2 - the results of measurements of the mass concentration of NP, obtained under conditions of intralaboratory precision, mg/DM 3 ;

R L - limit of intralaboratory precision, %. The values for the within-laboratory precision limit are shown in Table 4.

When condition (7) is satisfied, both measurement results are acceptable.

13.3.3 If condition (7) is not met, the experiment is repeated. If condition (7) is not met again, the reasons leading to the failure of condition (7) are found out and eliminated.

Table 4 - Measurement range, values of the limit of intralaboratory precision at a confidence level P = 0.95

13.4 Checking the acceptability of measurement results obtained under reproducibility conditions

13.4.1 The verification of the acceptability of the measurement results obtained under reproducibility conditions is carried out according to the results of measurements of the mass concentration of NP in the control samples prepared on the basis of standard samples of the composition of the NP solution.

13.4.2 The discrepancy between single measurement results obtained in two laboratories should not exceed the reproducibility limit.

where X and X 2 - the results of measurements of the mass concentration of OP, obtained under conditions of reproducibility, mg/DM 3 ;

R - reproducibility limit, %. Reproducibility limit values are shown in Table 5.

Table 5 - Measurement range, values of the reproducibility limit at a probability P = 0.95

When condition (8) is satisfied, both measurement results are acceptable.

If the reproducibility limit is exceeded, methods for checking the acceptability of measurement results can be used in accordance with section 5 of GOST R ISO 5725-6.

13.5 Algorithm for online control of the measurement procedure using control samples

13.5.1 Operational control of the measurement procedure is carried out by comparing the result of a single control procedure K k with the accuracy control standard K.

13.5.2 The result of the control measurement procedure K k is calculated by the formula

K K = |X - C|, (9)

where X is the result of the control measurement of the mass concentration of OP in the control sample, mg/dm 3 ;

C - certified value of the control sample, mg/dm 3 .

13.5.3 Control standard K is calculated using the formula

K = Δ L, (10)

where Δ l is the value of the measurement error characteristic, set in the laboratory when implementing the methodology, corresponding to the certified value of the control sample, mg/dm 3 . The value of the error characteristic is calculated by the formula

Δ l \u003d 0.01 × δ l × C, (11)

where δL is the relative value of the error characteristic of the measurement results, established in the laboratory when implementing the methodology, %.

13.5.4 The quality of the control procedure is recognized as satisfactory when the condition is met

K k £ K. (12)

If condition (12) is not met, the experiment is repeated. If condition (12) is not met again, the reasons leading to unsatisfactory results are clarified.

13.5.5 The frequency of operational control of the measurement procedure, as well as the ongoing procedures for monitoring the stability of the results of the measurements performed, are regulated in the laboratory documents.

Keywords: drinking water, natural water, treated waste water, oil products, hydrocarbons, mass concentration, IR spectrophotometry.

Development Manager: Director of PEP SIBECOPRIBOR LLC

Position name of the enterprise-developer

Co-performers:

Development Manager: Head of the Laboratory for Ecological Research and Chromatographic Analysis (LEiHA)

job title

The methodology for measuring the mass concentration of oil products was approved

name of the document on the approval of the measurement procedure

in drinking, natural and treated wastewater by the ___________ method

Fluorescent-photometric liquid analyzers "Fluorat-02" (hereinafter

Analyzers) are designed to measure the content of various components in liquid samples by photometric and luminescent methods.

Description

The principle of operation of the luminescence registration channel of analyzers is based on measuring the intensity of the light flux from the object under study, which occurs under the influence of exciting optical radiation of a selected spectral range or as a result of chemical reactions and registered by the photodetector of this channel. Photometric channel (transmission channel) of purpose analyzers for measuring the directional transmittance of the object under study.

The analyzers are designed in the form of desktop laboratory instruments and represent a single unit and consist of an optical radiation source (xenon lamp), optical circuit elements, a cell compartment with ports for light filters of the luminescence transmission and registration channels, photodetectors of the optical channels, a microprocessor system in which signal processing and measurement result calculation. Light from a radiation source operating in a pulsed mode passes through a light filter that selects the spectral region of excitation and enters a beam splitter plate, which divides the light flux into two channels: a reference channel and a luminescence excitation channel, which is also a photometric channel. In the reference channel, the radiation, bypassing the sample, enters the radiation receiver of this channel, forming an electrical comparison signal, which serves to correct the instability of the lamp operation from pulse to pulse. In the luminescence excitation/photometric channel, light passes through the test sample, causing it to luminesce, and then enters its photodetector. The electrical signal of this receiver depends on the directional transmittance of the object under study. In the luminescence registration channel, the radiation of the luminescent components of the object under study passes through a light filter that selects the spectral region of registration and enters the radiation receiver of the luminescence registration channel. The electrical signal of this receiver depends on the concentration and composition of the analytes in the solution and is called the luminescence signal.

Using the microprocessor system of the analyzers, the signals from the photodetectors of all channels are processed and the concentration of the analytes is calculated using a pre-set calibration characteristic.

The analyzers are produced in the following modifications:

"Fluorat-02-4M" - for measuring the directional transmittance and intensity of fluorescence, phosphorescence and chemiluminescence of samples, as a fluorimetric detector for chromatography;

"Fluorat-02-5M" - for measuring the directional transmittance and fluorescence intensity.

Both modifications of the analyzers have the same appearance, which is shown in Fig.1.

Software

The analyzers are equipped with a built-in software(Software) that controls the operation of the analyzer, processes and displays and stores the received data.

All software is metrologically significant and performs the following functions:

Performing self-diagnostics of analyzers;

Analyzer operation management;

Collection and processing of measurement information coming from photodetectors;

Calculation of directional transmittance and luminescence intensity of samples;

Calibration of analyzers and calculation of measurement results;

Saving measurement results and calibration characteristics in non-volatile memory.

The level of software protection against unintentional and intentional changes corresponds to the level "C" according to MI 3286-2010. The influence of software on metrological characteristics is taken into account when normalizing the latter.

Specifications

Spectral range of optical radiation, nm: modification "Fluorat-02-4M"

modification "Fluorat-02-5M"

excitation channel from 250 to 900

Sheet No. 3 Total sheets 5

bandwidth from 250 to 900

registration channel from 250 to 900

Limit of detection of control substance (phenol) in water, mg/dm3, no more than 0.005

Measurement range of mass concentration of control substance (phenol) in water, mg/dm3 from 0.01 to 25

Limits of permissible absolute error of the analyzer when measuring the mass concentration of the control

substances (phenol) in water, mg/dm3 ± (0.004 + 0.10 xC*)

Measurement range of directional transmittance, % from 5 to 100

Limits of permissible absolute error in measurements of the directional transmittance, % ± 2

Warm-up time, min, no more than 30

Time continuous work, h, not less than 8

Overall dimensions, mm, no more than 305x320x110

Weight, kg, not more than 6.5

AC supply voltage, V (220 ± 22)

Frequency, Hz (50 ± 1) Power consumption, VA, not more than 36 MTBF, h, not less than 2500 Average term service, years 5 Operating conditions:

Ambient temperature, °C from 10 to 35

Atmospheric pressure, kPa from 84 to 106.7

Relative humidity at a temperature of 25 °С %, no more than 80

* C - current value of the mass concentration of the control substance (phenol)

Type approval mark

applied to the front panel of the analyzers and/or nameplate and title page Operating manuals by computer graphics.

Completeness

Verification

is carried out according to the document MP-242-1556-2013 “Luminescent-photometric liquid analyzers “Fluorat-02”. Verification Methodology, approved by the GCI SI FSUE VNIIM im. DI. Mendeleev" April 25, 2013.

Basic means of verification:

Set of light filters KOF-02, number of the State Register SI 45802-10 (nominal values of the spectral directional transmittance at 520 nm 92; 71; 38; 27; 6%; the limit of the permissible basic absolute error of the spectral transmittance is ±0.5%);

GSO 8714-2005 composition of phenol solution (mass concentration of phenol 1 mg/cm3, PG

Information about measurement methods

GOST 18294-2004 Drinking water. Method for determining the content of beryllium GOST 31857-2012 Drinking water. Methods for determining the content of surfactants

GOST 31949-2012 Drinking water. Boron content determination method

GOST R 54499-2011 Drinking water. Luminescent content determination method

GOST R 55227-2012 Water. Methods for determination of formaldehyde content

FR.1.31.2012.13169 (PND F 14.1:2:4.128-98, edition of 2012) Method for measuring the mass concentration of oil products in samples of natural, drinking and waste water by the fluorimetric method on the Fluorat-02 liquid analyzer

FR.1.31.2012.13170 (PND F 16.1:2.21-98, edition of 2012) Method for measuring the mass fraction of oil products in soil and soil samples by the fluorimetric method on the Fluorat-02 liquid analyzer

FR.1.29.2006.02216 Methodology for measuring the mass concentration of formaldehyde in the air working area and atmospheric air populated areas fluorimetric method on the liquid analyzer "Fluorat-02"

Regulatory and technical papers, establishing requirements for luminescent-photometric liquid analyzers "Fluorat-02"

TU 4215-350-45549798-2013 "Luminescent-photometric liquid analyzers "Fluorat-02". Specifications".

when carrying out activities in the field of protection environment; when performing work to ensure safe conditions and labor protection; when performing work on conformity assessment of industrial products and products of other types, as well as other objects mandatory requirements, established by law Russian Federation.

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FEDERAL SUPERVISION SERVICE
IN THE SPHERE OF NATURE MANAGEMENT

QUANTITATIVE CHEMICAL ANALYSIS OF WATER

METHOD (METHOD) OF MEASUREMENTS OF MASS
CONCENTRATIONS OF PETROLEUM PRODUCTS AND FATS
(IN THEIR JOINT PRESENCE)
IN SAMPLES OF DRINKING, NATURAL AND
TREATED WASTEWATER
IR SPECTROPHOTOMETRY METHOD
USING KH SERIES CONCENTRATOMETER

PND F 14.1:2:4.273-2012

The technique is approved for purposes
state environmental control

MOSCOW
(Edition 2017)

The measurement technique is certified by the Federal State Autonomous educational institution higher education"National Research Tomsk politechnical University"(FGAOU HE "National Research Tomsk Polytechnic University") (Certificate of Accreditation No. 01.00143-2013 dated December 11, 2013), reviewed and approved by the Federal State Budgetary Institution "Federal Center for Analysis and Evaluation of Technogenic Impact" (FGBU "FCAO").

This edition of the methodology has been issued to replace the previous edition of PND F and is valid until the release of a new edition.

Information on the methodology was transferred to the Federal Information Fund for Ensuring the Uniformity of Measurements. Information about the methodology is presented on the websites http://www.fundmetrology.ru in the section "Information on certified measurement techniques (methods)" and http://www.fcao.ru in the section "Analysis methods".

Developer:

LLC "Industrial and ecological enterprise "SIBEKOPRIBOR"

Address: 630058, Novosibirsk, st. Russian, 41

1 PURPOSE AND SCOPE

This document establishes a method for measuring the mass concentration of oil products (hereinafter referred to as NP) and fats (hereinafter referred to as G) in their joint presence in samples of drinking, natural and treated waste water using KN series concentrators.

The measurement range for petroleum products is from 0.04 to 5 mg/dm 3 , for fats from 0.10 to 10 mg/dm 3 .

Nonionic surfactants (surfactants) at a mass concentration of less than 0.1 mg/dm 3 do not interfere with the determination of oil products and fats.

2 REGULATORY REFERENCES

Pipettes measured 1-2-2-1, 1-2-2-5, 1-2-2-10, 1-2-2-25 in accordance with GOST 29227

Measured test tubes P-2-25-14/23 XC according to GOST 1770

Cylinders 2-10-2, 2-25-2, 2-50-2, 2-1000-2 according to GOST 1770

4.2 Reference materials

When performing measurements, use:

State standard sample (GSO 7822-2000) of the composition of a solution of petroleum products (hydrocarbons) in carbon tetrachloride: certified value - mass of petroleum products (hydrocarbons) 50.00 mg; the limits of the absolute error of the certified value ± 0.25 mg at Р = 0.95;

State standard sample (GSO 7117-94) of the composition of petroleum products in a water-soluble matrix: certified value - the mass of petroleum products from 0.005 to 5.0 mg; the limits of the relative error of the certified value from 1.3 to 0.8% at P = 0.95;

State standard sample (GSO 9437-2009) of the composition of a mixture of triglycerides of fatty acids: certified value - mass fraction of the sum of triglycerides of fatty acids 99.6%; the limits of the absolute error of the certified value ±0.4% at P = 0.95;

State standard sample (GSO 10212-2013) of the mass concentration of fats in a water-soluble matrix (SO ZhVM-PA (2)). certified value - mass concentration of fats 2.00 g/dm 3 ; the limits of the relative error of the certified value are ±2.5% at P = 0.95.

4.3 Accessories

Drying cabinet for general laboratory, providing temperature maintenance from 105 to 110 °С

Muffle furnace PM-8 according to TU 79-337

Solvent distillation glass plant:

Dephlegmator 300-19 / 26-19 / 26 TC according to GOST 25336;

Refrigerator KhPT-1-300-14/23 XC according to GOST 25336;

Electric stove with a closed spiral according to GOST 14919;

Liquid glass thermometer type B with a range of measured temperatures from 0 to 150 °C in accordance with GOST 28498

Glass for weighing SV-14/8 in accordance with GOST 25336

Chromatographic glass column (inner diameter 7 mm, length 200 mm)

Stand for chromatographic columns

Laboratory extractor EL-1 ISHVZh.002 PS

Dividing funnels VD-3-500 XS, VD-3-1000 XS according to GOST 25336

Sieve with a hole diameter of 0.16 mm

Glass rods (12 - 15) cm long

Household refrigerator providing temperature (0 - 5) °C Glass bottles for sampling and storage of samples

4.4 Reagents and materials

Carbon tetrachloride (tetrachloromethane), chemically pure according to GOST 20288 or for extraction from aqueous media, chemically pure. on

Aluminum oxide for chromatography according to or analytical grade. according to GOST 8136

Fiberglass or glass wool according to GOST 10727

Universal indicator paper for determining pH by

Cotton wool medical hygroscopic in accordance with GOST 5556

Notes

1 The use of other IR analyzers, except for KN series concentrators, is not allowed.

2 It is allowed to use other measuring instruments (analytical balances, pipettes, volumetric utensils, sieve, etc.) and auxiliary equipment with metrological and technical characteristics not worse than those indicated. It is allowed to use reagents of similar or higher qualification, manufactured according to other regulatory documentation, including imported ones.

5 MEASUREMENT METHOD

The method for measuring the mass concentration of extractables (NP + L) is based on the dependence of the intensity C-H absorption bonds in the infrared region of the spectrum (2930 ± 70) cm -1 on the mass concentration of NP and F in a solution of carbon tetrachloride.

The analysis procedure consists in the extraction of NPs and L with carbon tetrachloride from the analyzed water sample (at pH ~ 2) by double extraction.

The extract is divided into two approximately equal parts. In the first part of the extract, the total concentration of all extracted substances is determined.

The second part of the extract is subjected to chromatographic separation in a column filled with aluminum oxide, and the mass concentration of NP is determined in the eluate.

Based on the difference in the results of these determinations, the total concentration of F in the analyzed water sample is found.

6 SAFETY AND ENVIRONMENTAL REQUIREMENTS

6.1 When performing measurements, it is necessary to comply with safety requirements when working with chemical reagents in accordance with GOST 12.1.007.

6.2 When working with the equipment, it is necessary to observe the electrical safety rules in accordance with GOST R 12.1.019, as well as the requirements set forth in technical documentation to the device being used.

6.3 The laboratory room must comply with fire safety requirements in accordance with GOST 12.1.004 and have fire extinguishing equipment in accordance with GOST 12.4.009. The content of harmful substances should not exceed the permissible concentrations in accordance with GOST 12.1.005.

6.4 The organization of training of workers in labor safety is carried out in accordance with GOST 12.0.004.

6.5 Disposal of used solutions after measurements are carried out in accordance with the "Instructions for Disposal of Solutions" developed by the organization.

6.6 Environmental protection requirements must comply with GOST 12.0.230.

7 OPERATOR QUALIFICATION REQUIREMENTS

To perform measurements and process their results, only specialists with higher or secondary specialized chemical education and experience in a chemical laboratory, who have undergone appropriate instruction, who have mastered the method in the process of training, and who have received satisfactory results of control measurements, are allowed.

8 REQUIREMENTS FOR MEASUREMENT CONDITIONS

When preparing solutions and preparing samples for measurements, the following external conditions are observed:

Ambient temperature from 15 to 25 °С;

Relative air humidity at 25 °С from 30 to 80%;

Atmospheric pressure from 630 to 800 mm Hg. Art. (from 84.0 to 106.7 kPa);

Measurements on the instruments are carried out under the conditions specified in the instruction manual for them.

9 PREPARATION FOR MEASUREMENTS

In preparation for measurements, the following work is carried out: sampling, preparation of glassware, reagents and materials, preparation of solutions, preparation of the concentrator, control of the stability of the calibration characteristic.

9.1 Sampling

9.1.1 Sampling is carried out in accordance with GOST 31861, GOST R 56237, GOST 17.1.4.01.

When sampling, the capture of the NP film from the surface of the water should be excluded. Water samples are taken in glass bottles. The container must be flushed with carbon tetrachloride before sampling. The collected samples are used completely and are not filtered.

The volume of the sample taken, depending on the expected mass concentration of NPs and F in water, must correspond to the values \u200b\u200bspecified in Table 2.

Table 2 - The volume of water samples depending on the expected mass concentration of NPs and F in water

9.1.2 Extraction of OP and F from water is carried out no later than 3 hours after sampling.

9.1.3 If it is impossible to carry out extraction during this period, the sample is preserved by adding a mixture of sulfuric acid and carbon tetrachloride at the rate of 1 cm 3 of concentrated sulfuric acid and (2.0 - 3.0) cm 3 of carbon tetrachloride per 1 dm 3 of the sample. When extracting these volumes should be taken into account. Preservatives may be added to the empty container prior to sampling. Preserved water samples can be stored at a temperature of (3 - 5) ° C for no more than 72 hours.

9.1.4 When sampling, an accompanying document is drawn up, which indicates:

Purpose of analysis, suspected contaminants;

Place, time of selection;

Sample number;

Position and surname of the specialist taking the sample, date.

9.2 Preparation of glassware, reagents and materials

9.2.1 Preparing glassware and measuring cell

When performing measurements of the mass concentration of NP and F, it is necessary to carefully observe the cleanliness of the chemical glassware.

For washing chemical dishes it is allowed to use concentrated sulfuric and nitric acids.

Do not use all types of synthetic detergents for washing.

Rinse the cuvette at least three times with carbon tetrachloride prepared according to 9.2.2.

9.2.2 Preparation of carbon tetrachloride

Check the purity of each batch of carbon tetrachloride in accordance with the instruction manual for the concentrator used.

If the reading does not exceed 20.0 mg / dm 3, then carbon tetrachloride is suitable for work. Otherwise, carry out the purification of carbon tetrachloride as follows.

About 0.4 dm 3 of carbon tetrachloride is placed in a separating funnel of the EL-1 extractor with a capacity of 1 dm 3, 0.5 dm 3 of distilled water is added and stirred for 1 minute. The carbon tetrachloride layer is poured into the flask. The procedure is repeated with a new portion of distilled water.

About 10 g of sodium sulfate is added to the washed carbon tetrachloride and, stirring occasionally, is kept for (10 - 15) minutes. Dehydrated carbon tetrachloride is decanted into a distillation flask and distilled at a temperature range from 76 to 78 ° C, collecting separately the first (50 - 60) cm 3 (then discarded), the main fraction (actually purified carbon tetrachloride) and leaving about 50 cm3 in the distillation flask 3 carbon tetrachloride.

When carrying out the purification of carbon tetrachloride in the extractor EL-1, they are guided by the passport for EL-1.

In the absence of the EL-1 extractor, it is allowed to carry out cleaning in a separating funnel by shaking.

9.2.3 Preparation of alumina

Aluminum oxide is sifted through a sieve and a fraction (0.16 - 0.25) mm is used. Then aluminum oxide is washed with carbon tetrachloride prepared according to 9.2.2 so that carbon tetrachloride covers the layer of aluminum oxide, then it is dried in a fume hood, calcined in a porcelain or quartz cup in a muffle furnace at a temperature of (550 - 600) ° C for 4 hours , cooled in an oven to (100 - 200) ° C, then placed in a desiccator and cooled to room temperature.

If alumina turns yellow when ignited, it is unsuitable for use. The shelf life of calcined aluminum oxide in a tightly closed container is 1 month.

Before use required amount calcined aluminum oxide is weighed, 3% (by mass) of distilled water is added, tightly closed, shaken for several minutes and kept for a day at room temperature.

9.2.4 Preparation of sodium sulfate

Before use, sodium sulfate is dried at a temperature of (105 - 110) ° C for 8 hours in an oven, cooled and stored in a desiccator. The shelf life is no more than 1 month.

9.2.5 Preparation of sodium chloride

Sodium chloride is calcined in a porcelain or quartz cup in a muffle furnace at a temperature of (550 - 600) ° C for 4 hours, then cooled. Calcined sodium chloride can be stored for no more than 1 month in a flask with a ground stopper.

9.2.6 Preparation of sulfuric acid solution 1:9

In a heat-resistant container, 9 volumes of distilled water and 1 volume of concentrated sulfuric acid are mixed. The acid is carefully added to the water. . Shelf life in a bottle with a ground stopper is 1 month at a temperature of (20 ± 5) °C.

9.2.7 Preparation of a solution of sulfuric (nitric) acid (1:1)

In a heat-resistant container, equal volumes of distilled water and concentrated nitric or sulfuric acid are mixed. The acid is carefully added to the water. . Shelf life in a bottle with a ground stopper is 1 month at a temperature of (20 ± 5) °C.

9.2.8 Preparing glass fibers or glass wool

Glass fiber or glass wool is kept in dilute (1:1) sulfuric or nitric acid according to 9.2.7 for 12 hours, washed with tap water, then with distilled water and dried in an oven. Before use, glass fibers or glass wool are thoroughly washed with carbon tetrachloride and dried at room temperature.

Note - It is allowed to use medical cotton wool in accordance with GOST 5556 (cotton, not synthetic!). Before use, cotton wool is thoroughly washed with carbon tetrachloride and dried at room temperature.

9.2.9 Preparing the chromatographic column

A layer (about 0.5 cm) of glass fiber or glass wool prepared according to 9.2.8 is placed in the lower (drawn) part of the washed and dried column. Then, 3 g of alumina prepared according to 9.2.3 is poured into the chromatographic column, and the glass fiber or glass wool layer is again placed. 10 cm 3 of carbon tetrachloride are passed through a chromatographic column. The first portion of the eluate (about 3 cm3) passed through the column of carbon tetrachloride is discarded. The next portion of the eluate is collected in a clean beaker. The measuring cuvette is preliminarily rinsed with a small amount of eluate, then it is filled and the mass concentration of OP in the eluate is measured in accordance with 10.3.

If the measured value of the mass concentration of OP in the eluate does not exceed 0.6 mg/dm 3 , then the chromatographic column is suitable for work. If the specified value is exceeded, the chromatographic column is washed again with a new portion of carbon tetrachloride and the measurement is repeated according to 10.3.

Aluminum oxide is used in the chromatographic column once.

9.2.10 Carbon tetrachloride recovery

Plums of carbon tetrachloride formed in the process of preparing the device for operation, rinsing dishes during preparation and during the determination, as well as after analyzing samples, are collected in a bottle for draining. When a sufficient amount of drains has accumulated, the solvent is cleaned using one of the following methods:

In accordance with MI "PEP "SIBEKOPRIBOR" No. 06-02 "Guidelines for the adsorption treatment of waste carbon tetrachloride";

After drying with sodium sulfate, it is distilled, collecting the middle fraction 3).

3) Plums of carbon tetrachloride containing GSO of the composition of the NP solution and a mixture of triglycerides of fatty acids are not subject to distillation!

Check the purity of the resulting carbon tetrachloride according to 9.2.2 and, if necessary, repeat the purification.

If in this way it is not possible to achieve the desired degree of purification, then carbon tetrachloride is not suitable for further use.

9.2.11 Preparation of purified distilled water

A sample of distilled water is extracted at the rate of 20 cm 3 of carbon tetrachloride per 1 dm 3 of water.

9.3 Preparation of solutions

9.3.1 Preparation of the main solution of NP mass concentration of 1000 mg / dm 3

The main solution of NP in carbon tetrachloride is prepared from the GSO 7822-2000 composition of the solution of NP (hydrocarbons) in carbon tetrachloride 4) . For this, the GSO of the composition of the NP solution from the ampoule is quantitatively transferred into a volumetric flask with a capacity of 50 cm 3, then the ampoule is thoroughly washed 5 times with carbon tetrachloride in portions of 3 cm 3, poured into a volumetric flask, and then the volume of the solution in the flask is brought to the mark with carbon tetrachloride and carefully mixed.

4) It is allowed to use the GSO of the composition of the solution of NP (hydrocarbons) in carbon tetrachloride of another type with similar metrological characteristics. In this case, the stock solution is prepared in accordance with the instructions for use of the GSO used.

The mass concentration of HP in the resulting solution is 1000 mg/DM 3 .

The solution can be stored at a temperature of (0 - 5) ° C for no more than 6 months. Before use, the solution is kept at room temperature for at least 30 minutes.

The main solution is prepared again in case of a change in the batch of carbon tetrachloride.

The main solution of NP is used as an additive in quality control of measurement results.

9.3.2 Preparation of a working solution of NP mass concentration of 100 mg / dm 3

The mass concentration of NP in the resulting solution is 100 mg/DM 3 .

The solution can be stored at a temperature of (0 - 5) ° C for no more than 1 month. Before use, the solution is kept at room temperature for at least 30 minutes.

The working solution is used to set the initial values in accordance with 9.4.

9.3.3 Preparation of NP calibration solutions

Calibration solutions of NP in carbon tetrachloride are prepared immediately before use by diluting the working solution of NP.

To do this, pipette 1.0 into volumetric flasks with a capacity of 50 cm 3; 2.5; 5.0; 25.0 cm 3 of the working solution of NP and bring the volumes of solutions in flasks to the mark with carbon tetrachloride. The solutions are thoroughly mixed.

The mass concentration of oil products in the resulting solutions is 2, 5, 10, 50 mg/dm 3 respectively. The relative error in the preparation procedure does not exceed 2%.

Calibration solutions are used to control the performance of the concentrator in the range of measured values of mass concentrations of analytes.

9.3.4 Preparation of the stock solution of a mixture of triglycerides of fatty acids with a mass concentration of 1000 mg / dm 3

50 mg GSO 9437-2009 5) of the composition of the mixture of triglycerides of fatty acids are placed in a volumetric flask with a capacity of 50 cm 3, dissolved in carbon tetrachloride and the volume of the solution in the flask is adjusted to the mark with carbon tetrachloride, mixed.

5) It is allowed to use the GRM composition of a mixture of triglycerides of fatty acids of another type with similar metrological characteristics. In this case, the preparation of the stock solution should be carried out in accordance with the instructions for use of this GSO.

The mass concentration of triglycerides of fatty acids in the resulting solution is 1000 mg/DM 3 .

The relative error in the preparation procedure does not exceed 0.5%.

The main solution is allowed to be stored at a temperature of (0 - 5) ° C for no more than 6 months. Before use, the solution is kept at room temperature for at least 30 minutes.

The stock solution of a mixture of fatty acid triglycerides is used as an additive in quality control of the measurement results.

9.4 Preparing the concentrator

Preparation for operation, setting the initial values and monitoring the performance of the KN series concentrator is carried out in accordance with the operating manual.

To set the initial values, carbon tetrachloride is used, which is used in the analysis, and a working solution of oil products with a mass concentration of 100 mg / dm 3, prepared from the same carbon tetrachloride.

9.5 Checking the stability of the calibration characteristic

The stability of the calibration characteristic is checked immediately after setting the initial values according to 9.4.

The check consists in measuring the mass concentration of NP in one or more solutions (9.3.3) in the "PETROLEUM PRODUCTS" mode.

The mass concentration of NP in the prepared sample is measured and compared with the certified value of the mass concentration of NP in the calibration solution. For each solution, at least two measurements of the mass concentration of OP in calibration solutions are carried out. The first measurement result is not taken into account.

The calibration characteristic is considered stable if the following condition is met for each calibration solution:

If the condition of stability of the calibration characteristic is not met only for one calibration solution, it is necessary to re-measure this solution in order to exclude a result containing a gross error.

If the calibration characteristic is unstable, find out and eliminate the causes and repeat the control using other samples provided by the procedure.

Control of the stability of the calibration characteristics is carried out at least once a quarter or when changing batches of reagents.

10 MAKING MEASUREMENTS

10.1 Extraction

The sample of the analyzed water is completely transferred to the separating funnel of the EL-1 extractor of the appropriate capacity, dilute (1:9) sulfuric acid, prepared according to 9.2.6, is added to pH ~ 2 (control by indicator paper). If the water sample has been previously preserved in accordance with 9.1.3, then sulfuric acid is not added. Then add 40 g of sodium chloride, prepared according to 9.2.5, per 1 dm 3 of the water sample. The container in which the sample was located is thoroughly rinsed with 5 cm 3 of carbon tetrachloride and the solvent is poured into a separating funnel. Another 5 cm 3 of carbon tetrachloride are added there (taking into account conservation, the total volume of carbon tetrachloride in the separating funnel should be 10 cm 3).

Extraction is carried out using an EL-1 extractor for at least 5 minutes at a stirrer rotation speed of ~2500 rpm. When carrying out extraction, it is necessary to ensure that the extractant is evenly distributed throughout the entire volume of the water sample, then the water sample is settled for (10 - 15) minutes to separate the aqueous and organic phases. After phase separation, the lower layer (extract) is poured into a flask. Repeat the extraction with a new portion of carbon tetrachloride with a volume of 10 cm 3 . The extracts are then combined and treated according to 10.2 or stored.

The extract can be stored for 1 week at a temperature of (3 - 4) °C. The volume of the analyzed water sample is measured with a measuring cylinder.

When carrying out extraction using the extractor EL-1, they are guided by the passport for EL-1. In the absence of the EL-1 extractor, it is allowed to carry out extraction in a separating funnel by shaking the water sample for 10 minutes.

10.2 Extract processing

10.2.1 Drying the extract

The extract is dried with sodium sulfate (not less than 4 g), prepared according to 9.2.4, for 10 minutes, adding it to the beaker in small portions while stirring the contents with a glass rod. After the drying process is completed, the extract is poured into a measuring cylinder with a capacity of 25 cm 3 , then it is divided into two approximately equal parts (extract No. 1 and extract No. 2).

10.2.2 Preparation of the extract to determine the total mass concentration of OP and F

Extract No. 1 is poured into a measuring cuvette, which is pre-rinsed with this solution, and the total mass concentration of OP and F is measured in accordance with 10.3.

If the mass concentration of NPs and F in the analyzed extract exceeds the upper limit of the measurement range of the device, then the extract is diluted with carbon tetrachloride, prepared according to 9.2.2, and extract No. 1A is obtained. Then extract No. 1A is poured into a cuvette, which is pre-rinsed with this solution, installed in the instrument and a second measurement is made in accordance with 10.3.

Note - Dilution of extract No. 1 is carried out (no more than 20 times) in such a way that the total mass concentration of the analytes (NP and G) corresponds to the regulated measurement range of the device.

Extract No. 1A is used to determine the mass concentration of OP in accordance with 10.2.3.

10.2.3 Preparation of the extract for determination of the mass concentration of OP

If the total mass concentration of OP and F in the analyzed extract No. 1 does not exceed the upper limit of the instrument range, then extract No. 2 is used.

If dilution according to 10.2.2 was required to measure the total mass concentration of NP and G, then extract No. 1A is used.

Pour 3 cm 3 of carbon tetrachloride into a chromatographic column prepared according to 9.2.9 for wetting. As soon as carbon tetrachloride is absorbed into aluminum oxide, then extract No. 2 (or extract No. 1A) is passed into the chromatographic column. Care must be taken that the liquid level does not fall below the top layer of aluminum oxide. Discard the first 3 cm 3 of the eluate, and collect the remainder of the eluate in a measuring cylinder with a capacity of (10 - 25) cm 3 and use it to measure the mass concentration of the NP in accordance with 10.3.

10.3 Taking measurements

Measurements are carried out in accordance with the operating manual of the concentrator.

10.3.1 The measuring cuvette prepared according to 9.2.1 is pre-rinsed with a small amount of the analyzed solution (extract No. 1, extract No. 1A or eluate obtained according to 10.2).

10.3.2 Fill the cuvette with the analyzed solution, install it in the instrument and measure the mass concentration of the extracted substances, reading the instrument readings.

10.4 Determination of NP and F in a blank

Before analyzing a series of samples, the mass concentration of NPs and F in a blank sample is determined.

To do this, take 1.0 dm 3 of distilled water purified according to 9.2.11 and process it as described in 10.1 - 10.2. Measure the mass concentration of the extractables (NPs and Gs) in the solution in accordance with 10.3.

If the measured value of the mass concentration of extractables in the analyzed solution is a negative number, then it is necessary to carry out the purification of carbon tetrachloride according to 9.2.2. Then repeat the procedure for preparing solutions in accordance with 9.3 and set the initial values in accordance with 9.4.

If the value of the mass concentration of NPs and F in a blank sample exceeds 0.02 mg/dm 3, then the determination is repeated in accordance with 10.1 - 10.2 and, if necessary, the cause of contamination of the blank sample is identified and eliminated.

The results of the analysis of a blank sample are taken into account when calculating the mass concentration of NPs and F in the sample. The analysis of a blank sample is also carried out when using a new batch of reagents.

11 PROCESSING THE RESULTS OF MEASUREMENTS

11.1 Measurement result - mass concentration of extracted substances (petroleum products and fats (NP + F)), X(NP + W), mg / dm 3, in the analyzed water sample is calculated by the formula

where X(NP + W) ISM - the result of measuring the mass concentration of extracted substances of oil products and fats on the concentrator, mg/dm 3 ;

V EC - the volume of carbon tetrachloride used for extraction ( V EC = 20 cm 3);

K P is the dilution factor, i.e. the ratio of the volumes of the volumetric flask and the aliquot of the extract (taken into account when diluting according to 10.2.2);

X(NP + W) HOL - the result of measuring the mass concentration of oil products and fats in a blank sample, mg / dm 3 in terms of the volume of a sample of distilled water.

The result of measuring the mass concentration of oil products and fats in a blank sample, X(NP + F)CHOL, mg / dm 3, calculated by the formula

where X(NP)ISM - the result of measuring the mass concentration of oil products on the concentration meter, mg/dm 3 ;

V EC - the volume of carbon tetrachloride used for extraction ( V EC \u003d 20 cm 3), cm 3;

K P is the dilution factor, i.e. the ratio of the volumes of the volumetric flask and an aliquot of the extract (taken into account when diluting it according to 10.2.2);

V PR - the volume of the analyzed water sample, cm 3;

X(NP)CHOL - the result of measuring the mass concentration in a blank sample of oil products, in terms of the volume of a sample of distilled water, mg / dm 3.

Mass concentration measurement result X(NP)CHOL in a blank sample, mg / dm 3, calculated by the formula

where X (NP + W) - mass concentration of all extracted substances, calculated by formula (3), mg / dm 3;

X (NP) - mass concentration of oil products, calculated by the formula (5), mg / dm 3.

11.4 The result of a single measurement is taken as the result of the analysis of the mass concentration of oil products and fats in the sample.

12 PRESENTATION OF MEASUREMENT RESULTS

12.1 The measurement results are recorded in the test report, which is drawn up in accordance with GOST ISO / IEC 17025.

The results of measurements of the mass concentration of NP or F, X, mg / dm 3 , are presented in the form (with laboratory-confirmed compliance of the analytical procedure with the requirements of this document)

where X- the result of measurements of the mass concentration of NP or F, obtained in accordance with procedures 10.1 - 10.3, mg / dm 3;

Δ - absolute error in measuring the mass concentration of NP or W, mg / dm 3, calculated by the formula

U- expanded uncertainty at k = 2, mg/dm 3 , calculated by the formula

where U (rel) - expanded uncertainty (in relative units), %. Values U (rel) for k = 2 are given in Table 1.

Note - The numerical values of the measurement result end with a digit of the same digit as the value of the accuracy indicator of the measurement procedure (the absolute error in measuring the mass concentration of oil products and fats).

12.2 It is permissible to represent the result of measurements in the form

provided that Δ l< Δ,

where Δ l is the value of the measurement accuracy indicator (confidence limits of the absolute measurement error) established during the implementation of this technique in the laboratory and ensured by monitoring the stability of the measurement results;

on condition U l< U,

where U l - the value of the expanded uncertainty, established during the implementation of this technique in the laboratory and provided by the control of the stability of the measurement results in the laboratory.

13 PROCEDURES TO ENSURE MEASUREMENT RELIABILITY

Ensuring the reliability of measurements is organized and carried out by checking the acceptability of measurement results obtained under reproducibility conditions, operational control of the measurement procedure and control of the stability of measurement results in accordance with GOST R ISO 5725 and RMG 76.

13.1 Checking the acceptability of measurement results obtained under reproducibility conditions

13.1.1 The verification of the acceptability of the measurement results obtained under reproducibility conditions is carried out according to the results of measurements of the mass concentration of NPs and F in samples for control, prepared on the basis of standard samples of the composition of the NP solution and standard samples of the composition of a mixture of triglycerides of fatty acids.

GSO 7117-94 for the composition of oil products in a water-soluble matrix and GSO 10212-2013 for the mass concentration of fats in a water-soluble matrix (SO ZhVM-PA (2)) are used as control samples (OK).

You can also use GSO 7822-2000 for the composition of a solution of petroleum products (hydrocarbons) in carbon tetrachloride and GSO 9437-2009 for the composition of a mixture of triglycerides of fatty acids (certified mixtures prepared from a basic solution of petroleum products and fats with a mass concentration of 1000 mg / dm 3 according to 9.3.3 and 9.3 .4), certified according to the preparation procedure according to RMG 60.

13.1.2 The discrepancy between single measurement results obtained in two laboratories should not exceed the reproducibility limit

where X 1 and X 2 - the results of measurements of the mass concentration of OP and F, obtained under conditions of reproducibility, mg/dm 3 ;

R- reproducibility limit, expressed in relative units. Relative values of the reproducibility limit are given in Table 3.

Table 3 - Measurement range, reproducibility limit values at probability P = 0.95

When condition (13) is satisfied, both measurement results are acceptable. If the reproducibility limit is exceeded, methods for checking the acceptability of measurement results can be used in accordance with section 5 of GOST RISO 5725-6.

13.2 Online control of the measurement procedure using control samples

The frequency of obtaining the results of control procedures and the forms of their registration are given in the laboratory documents that establish the procedure and content of work on the organization of methods for monitoring the stability of measurement results within the laboratory.

13.2.1 Operational control of the measurement procedure is carried out according to the following scheme:

Carrying out a control measurement and obtaining the result of the control procedure;

Calculation of the result of the control procedure ( Kk);

Calculation of the control standard ( To).

Implementation of the decisive control rule - comparison of the result of the control procedure with the control standard and conclusions based on the control results.

13.2.2 GSO 7117-94 for the composition of oil products in a water-soluble matrix and GSO 10212-2013 for the mass concentration of fats in a water-soluble matrix (SO ZhVM-PA (2)) are used as OK.

You can also use GSO 7822-2000 for the composition of a solution of petroleum products (hydrocarbons) in carbon tetrachloride, GSO 9437-2009 for the composition of a mixture of triglycerides of fatty acids (certified mixtures prepared from a basic solution of petroleum products and fats with a mass concentration of 1000 mg / dm 3 according to 9.3.3 and 9.3 .4), certified according to the preparation procedure according to RMG 60.

Control samples are samples obtained by adding GSO 7117-94 and GSO 10212-2013 or certified mixtures prepared from GSO 7822-2000 and GSO 9437-2009 to distilled water. The samples are prepared in the vessel where the extraction will take place. Sample analysis is carried out in accordance with the measurement procedure.

13.2.3 Result of the measurement control procedure Kk, mg / dm 3, calculated by the formula

where Δ is the error characteristic of the control measurement results, corresponding to the certified value of the control sample, mg/dm 3 .

The value of the error characteristic is calculated by the formula

where δ is the relative error in measuring the mass concentration of oil or liquid, %. The values of δ are given in Table 1.

13.2.5 Implementation of decision control rule

|Kk| ≤ To

If this condition is not met, the control procedure is repeated. If condition (17) is not met again, the reasons leading to an unsatisfactory result are found out and measures are taken to eliminate them.

Bibliography

TU 4215-011-39120772-2009 Concentrator KN-3. Specifications.

TU 4215-010-39120772-2009 Concentrator KN-2m. Specifications.

ISHVZh.004 TU Concentrator KN-2. Specifications.

TU 79-337-72 Muffle furnace PM-8. Specifications.

TU 2631-027-4449317-98 Chemically pure carbon tetrachloride (tetrachloromethane) for extraction from aqueous media. Specifications.

TU 6-68-164-99 Aluminum oxide for chromatography AOK-63-21. Specifications.

TU 6-09-1181-89 Universal indicator paper for determining pH 1 - 10 and 7 - 14. Specifications.

Development manager:
Director of PEP SIBECOPRIBOR LLC		SOUTH. Vasilenko

Artists:
Chief metrologist of PEP SIBEKOPRIBOR LLC		G.N. Ornatskaya

Co-performers:
Development manager:
Head of the Laboratory of Ecological Research and chromatographic analysis (LEiHA) NIOKh them. N.N. Vorozhtsov SB RAS
		S.V. Morozov

Senior Researcher		E.I. Chernyak

APPROVED	Quantitative chemical analysis water. Technique (method) of measurements mass concentration oil products and fats (with their joint presence) in samples drinking, natural and treated wastewater method IR spectrophotometry using KN series concentrators
Head of the enterprise-developer Director of PEP SIBECOPRIBOR LLC		SOUTH. Vasilenko

CJSC NPO "CHRISMAS-CENTER" has a wide database of regulatory and methodological documents and reference literature on the issues of eco-analytical and sanitary control of the following components: water, air, industrial emissions, soil and food, documents on labor protection and safety production processes.

Lists of regulatory and methodological documents are necessary for manufacturing industries, construction, research purposes.

The general list of documents contains information on almost all standardized methods of chemical, sanitary analysis, labor protection and hygiene, fire safety, radiation hygiene, microbiological analysis and much more.

Our company offers you to purchase regulatory and methodological documents and reference literature on the following sections:

methods of quantitative chemical analysis atmospheric air , air of the working area and emissions into the atmosphere - PND F 13. ..., M-MVI ...
methods of quantitative chemical analysis of drinking, natural and waste waters- PND F 14. ..., M-MVI, NDP, TsV, RD 52.24 ...
methods of quantitative chemical analysis of soils, waste, bottom sediments and rocks- PND F 16. ..., M-MVI, TsV, RD 52.18 ...
documents on sanitary control of atmospheric air, working area air and industrial emissions - SanPiN, SP, MUK, MU, GN
documents on sanitary and microbiological analysis of water- MU, MUK, SanPiN, SP, GN, R
documents on soil sanitary analysis and sanitary supervision over the collection, storage and disposal of waste
documents on food hygiene control- SanPiN, MUK, MU, GN
methods for calculating emissions into the atmosphere, methodological documents and reference literature
methods for calculating the volumes of waste generation, reference documents on the generation and disposal of waste and other thematic regulatory and methodological documents
documents on radiation hygiene and radiation safety
documents regulating the physical and chemical factors of the production and environment - GN, SanPiN, MUK, MU, SP
general documents Ministry of Health for Epidemiology, Toxicology, Hygiene and Sanitation - SP, SanPiN, MUK, MU, R, GN
recommendations for interstate standardization- RMG
recommendations for metrology- MI
documents on occupational health and safety of production processes- RD, PB, POT, POT RO, POT RM, TI
documents on occupational health- MUK, SanPiN, MU, SP, GN, MR
the documents Gosstroy of Russia- SNiPs, SP, MDS, RDS
the documents State fire service Ministry of Internal Affairs of Russia - NPB

The base of normative-methodical documents and reference literature is regularly updated. Only a part of the available literature is listed here, you can download the full list of regulatory and methodological documents and reference literature supplied by CJSC NPO "Chrismas-Center".

Current prices You can find out about the supplied documents by sending a list of items you are interested in to our office in a convenient way for you.

Currently, the Russian Federation has developed hundreds, if not thousands, of collections of regulatory and methodological documents, from which a clear hierarchical system has been built, which is sometimes only within the power of specialized highly professional lawyers to deal with.

Among such documents are:

Sanitary Rules and Norms (abbreviated SanPiN)
MVI - measurement techniques
SP ( sanitary rules)
MU (or otherwise MUK) - guidelines
GN ( hygiene standards)
MR (guidelines)
recommendations concerning interstate standardization - RMG
metrology recommendations - MI
other regulations, mandatory and recommended for execution.

Who publishes SanPiNs, PND F and other regulatory documents.

Organizations belonging to various departments issue such orders and periodically update them.

These departments include:

Ministry of Health care
Ministry of Environment and natural resources
Gosstroy of Russia
State Fire Service
State Committee Russian Federation for Environmental Protection,

And also in the regulation of natural normative documents of federal ( further PND F or PNDF) many other state institutions are also involved.

HDPEF literature is coming about a separate block of regulatory documents.

PND F is an abbreviation that stands for - environmental regulations federal (PND F). They are designed for quantitative chemical analysis and assessment of the state of environmental objects, for the purpose of state environmental control and monitoring. Let's take a look at the regulations in more detail.

List of normative and methodological documents PND F in force on the territory of the Russian Federation

One can write a lot about the fact that the regulatory and methodological documents that regulate environmental activities in our country are outdated, since they were adopted a very long time ago and have not been revised since then.

So, for example, the “Instruction on the procedure for conducting an environmental review of air protection measures and assessing the impact of atmospheric air pollution on design decisions” was adopted back in 1994.

In fairness, it should be noted that many of these documents are periodically reviewed by updating them, which contributes to their greater compliance with today's requirements.
Currently, as of 2015, the lists of methods included in the Register of PND F include:

1. List of methods for quantitative chemical analysis (QCA) of water.
Only in this list there are about 200 different documents and methods that allow measuring the mass concentration of pollutants in drinking, natural and waste waters. More than four dozen different research and production enterprises, inspections, budgetary institutions take part in the development of regulatory and methodological documents. We are talking about establishments located as in large scientific centers(Moscow, St. Petersburg), and in other cities of Russia (Obninsk, Bryansk, Novosibirsk, Tomsk, Vladivostok and Nizhny Novgorod). One of the most important regulatory documents of the PNDF regarding the methods of quantitative chemical analysis of water, approved for the purposes of state environmental control, is -.

2. List of methods for CCA of soils and wastes.
For complex analysis the state of the surface layer of the land, as well as substances recognized as unsuitable for further use, more than 80 methods have been developed so far. Soils can be tested for mercury, cadmium, and lead, as well as titanium, nickel, arsenic, and other periodic table elements.

The list of organizations developing methods is also somewhat more modest - it includes about 30 organizations.

One of the most important regulatory documents of PND F, regarding the quantitative chemical analysis of soils and wastes, approved for the purposes of state environmental control are

3. List of CCA methods for atmospheric air, industrial emissions into the atmosphere and air of the working area.
76 techniques are designed to ensure that the air that Russians breathe is clean and does not cause various diseases. There are methods among them that were developed about 20 years ago - for example, one of the most "ancient" instructions developed by a research institute from St. Petersburg under the appropriate name "Atmosphere" explains the procedure for measuring the mass concentration of the following substances in industrial emissions:

acetone (C 3 H 6 O),
ethanol (C 2 H 5 OH),
butanol (C 4 H 9 OH),
toluene (C 6 H 5 CH 3),
ethyl acetate (C 4 H 8 O 2),
butyl acetate (C 6 H 12 O 2),
isoamyl acetate (C 7 H 14 O 2),
ethyl cellosolve (C 4 H 10 O 2),
cyclohexanone (C 6 H 10 O).

The most recent is dated 2015 and concerns measurements of the mass concentration (C 20 H 12) of benzo (a) pyrene - it replaced another instruction that was issued in 1998 and updated in 2004. Its author is also an enterprise from St. the name of "Lumex-marketing" LLC. Almost all PND F are periodically updated.

Regarding the quantitative chemical analysis of atmospheric air, industrial emissions into the atmosphere and air of the working area, approved for the purposes of state environmental control

4. List of methods of toxicological control.
It's relative new sphere for control - it has only 15 instructions, many of which have been adopted in the last few years. Using them, it is possible to determine the toxicity of drinking, fresh natural water and wastewater, as well as soil, sediment and waste.

5. General questions.
The 10 guidelines in this section explain how samples should be taken and prepared. In addition, it contains documents that establish safety rules for conducting various studies, which is important, especially when working with harmful drugs. About 15 organizations involved in standardization work in this area.

Methods PND F

As is known, the authorities adhere to a unified scientific and technical policy in the field concerning the implementation of environmental control throughout Russia.

As part of this approach, Rosprirodnadzor subdivisions maintain a Register of methods for quantitative chemical analysis and assessment of the state of environmental objects approved for state environmental control and monitoring.

This register was put into effect on September 23, 1995, at the moment it is the only source of information on how to correctly measure certain indicators.

Only these methods can be used in order to carry out state environmental control to ensure safe nature management and the proper level of environmental protection.

Each technique, which is placed in the registry, has two numbers. The first is the registration code of the measurement technique according to the Federal Register. The second one simply designates and names the document.

Moreover, based on the second number, you can accurately determine what exactly is to be determined.

Here are some examples:

If this PND F 14, then a quantitative chemical analysis of the waters is carried out.
When it comes to PND F 16, then soils, wastes, bottom sediments and rocks are analyzed.
PND F 13 deals with the analysis of atmospheric air and industrial emissions.

All measurement methods included in the Register have been certified in full compliance with the requirements of the current Russian legislation and GOSTs.

Each technique has a certificate of metrological certification.

So, for the whole of 2014 and the past 8 months of 2015, were certified or new edition 2 methods related to testing atmospheric air, 8 - regarding testing various types water, 4 for improved soil quality assessment, 6 for toxicological analysis and 2 for general issues. With the release of new methods, the old ones lose their relevance, lose their force and are canceled.

How to buy HDPE F

Laboratories are the main buyers of normative methods.

Such divisions for scientific and technological experiments and checks can be located both at large manufacturing enterprises and serve exclusively its needs, or be independent and provide their services to many small companies.

Each of the options has its own advantages and disadvantages.

Without going into details of each of them, it can only be noted that the transfer of such control functions to outsourcing is accepted by the management of the enterprise after analyzing all the factors, based primarily on economic feasibility such actions.

In order for the laboratory to use one or another technique included in the Register, it must be purchased.

Environmental regulations n surfing the Internet is problematic, if not impossible. The use of methods in this case will not be legal. In order for the laboratory to be able to conduct certain studies, it needs to acquire methods from reliable sources, which are:

Method developers. Each research institute, educational and scientific institutions and other organizations that have certified methods in their assets have the right to implement it.
Federal State Budgetary Institution "Federal Center for Analysis and Assessment of Technogenic Impact" (FGBU "FTsAO"), related to the structure Federal Service on supervision in the field of nature management. There is a whole list of methods that can be implemented by this organization, which they are actively engaged in.
A large number of suppliers, whose activities include, among other things, the trade in techniques.

As for the pricing policy, first of all, the cost depends on the type of technique that needs to be purchased. So, one of the most expensive methods, passing in the Register under the PND F 13.1.3-97 code and the Federal number FR.1.31.2013.16442, is called "Method for measuring the mass concentration of sulfur dioxide in exhaust gases from boiler houses, thermal power plants, state district power plants and other fuels burning units. Its price is more than 20 thousand rubles.

Approximately the same price will cost the buyer and the methodology, passing under the numbers PND F 13.1.31-2002 and FR.1.31.2013.16461 and bearing the name "Method for measuring the mass concentration of hexavalent chromium in industrial emissions by the photometric method." One of the most inexpensive - PND F 12.1.1 - 99 " Guidelines for sampling when determining the concentration of harmful substances (gases and vapors) in emissions industrial enterprises"- is estimated at a cost of up to 3 thousand rubles.

If the methodology (PND F) is needed solely for initial familiarization, then its purchase on the Internet can cost several hundred rubles, but it should be remembered that in this case its purchase does not give the right to conduct certain studies.

PND F regulating the content of oil products in water

Answering the question about why regular checks of the content of oil products in water are needed, I would like to recall that high concentrations of oil products can have a narcotic effect and cause acute poisoning; petroleum products containing a small amount of aromatic hydrocarbons cause anesthesia and convulsions; a high content aromatic hydrocarbons can threaten chronic poisoning.

This issue is regulated by PND F 16.1;2.2.22-98 "Methodology for measuring the mass fraction of oil products in mineral, organogenic, organomineral soils."

The technique is designed to measure the mass fraction of oil products in mineral (sands, sandy loams, loams, clays), organogenic (peat, forest litter), organo-mineral soils and bottom sediments by IR spectrometry on oil product analyzers with their content from 50 to 100,000 mg / kg. In addition to these data, the methodology contains requirements for measuring instruments and auxiliary equipment, laboratory glassware, reagents and materials, as well as safety requirements and qualifications of the performer. Separately, the stage of preparation for the measurement, as well as the procedure for their implementation and processing of the results, is prescribed.

IPA F concerning sampling

No one will argue that correct sampling is the first and one of the most milestones in order to obtain accurate and true results. To understand this issue, it is necessary to purchase PND F 12.1: 2: 2.2: 2.3: 3.2-03 "Sampling of soils, soils, bottom sediments, silts, sewage sludge, industrial waste water sludge, production and consumption wastes". The methodology was developed by the Federal State Budgetary Institution "Federal Center for Analysis and Assessment of Technogenic Impact" and has been in force since 2014. It contains information on how to prepare dishes for sampling, how to select, transport and store soils and soils, how to take samples of precipitation, activated sludge from sludge and silt pads, liquid precipitation, bottom sediments of reservoirs and many other useful information which must be taken into account when conducting such studies.

Within the framework of one article, it was difficult to talk about all the variety of documents that are hidden under the mysterious abbreviation PND F, because their number exceeds four hundred. However, we are confident that we were able to somewhat expand the awareness of our readers in the hierarchical system of regulatory and methodological documents and bring more clarity to the topic under consideration.

PND F 14.1:2:4.128-98

QUANTITATIVE CHEMICAL ANALYSIS OF WATER

THE METHOD FOR MEASURING THE MASS CONCENTRATION OF PETROLEUM PRODUCTS IN SAMPLES OF NATURAL, DRINKING, WASTE WATER BY THE FLUORIMETRIC METHOD ON THE "FLUORAT-02" LIQUID ANALYZER

APPROVE

Deputy Chairman of the State Committee of the Russian Federation for Environmental Protection A.A.Solovyanov

The methodology is approved for the purposes of state environmental control

The methodology was reviewed and approved by the Main Directorate for Analytical Control and Metrological Support of Environmental Activities (GUAK) and the Chief Metrologist of the State Committee for Ecology of Russia.

Chief Metrologist of the State Committee for Ecology of Russia

Head of GUAC G.M. Tsvetkov

Developer: LLC "Lumex"

INSTEAD OF PND F 14.1:2:4.35-95

1. INTRODUCTION

This document establishes a methodology for performing measurements (hereinafter referred to as MVI) of the mass concentration of oil products in samples of natural, drinking and waste waters by the fluorimetric method on the Fluorat-02 liquid analyzer.

The measurement range of mass concentration of oil products is 0.005-50 mg/dm.

Fats, humic substances, saturated hydrocarbons of natural origin do not interfere with the determination of petroleum products. The method does not provide the error characteristics given in paragraph 2 when determining light oil products (gasoline) in waters, as well as individual compounds that are part of oil products.

When analyzing samples of raw wastewater from the pulp and paper, chemical industries, as well as according to the results of monitoring the transmittance of the hexane extract of the sample (item 9), additional purification of the extract on a chromatographic column filled with aluminum oxide is required.

2 ASSIGNED CHARACTERISTICS OF MEASUREMENT ERROR AND ITS COMPONENTS

The measurement technique provides measurement results with an error not exceeding the values given in Table 1.

Table 1 - Values of the indicator of repeatability, reproducibility, correctness and accuracy


Measurement range, mg/dm
From 0.005 to 0.01 incl.
Over 0.01 to 0.5 incl.
Over 0.5 to 50.0 incl.

Note. The following symbols are used in the table: - repeatability indicator (relative value of the standard deviation of repeatability), - reproducibility indicator (relative value of the standard deviation of reproducibility), ± - indicator of correctness (limits of relative systematic error at probability = 0.95), ± - indicator accuracy (limits of relative error at probability = 0.95).

The values of the accuracy index of the methodology are used for:

registration of measurement results issued by the laboratory;

assessment of the quality of testing in the laboratory;

evaluating the possibility of using the measurement results in the implementation of the methodology for performing measurements in a particular laboratory.

3 MEASURING INSTRUMENTS, AUXILIARY DEVICES, REAGENTS AND MATERIALS

When performing measurements of the mass concentration of oil products, the following measuring instruments are used, auxiliary devices, materials and solutions.

3.1 Measuring instruments


Liquid analyzer "Fluorat-02"		TU 4321-001-20506233-94
Scales laboratory special or high class accuracy with division value not more than 0.1 mg, maximum weighing limit not more than 210 g
________________ GOST R 53228-2008
Pipettes with one mark of the 2nd class of accuracy with a capacity of 10 cm3
Graduated pipettes of the 2nd accuracy class with a capacity of 1, 2, 5 cm3
Volumetric flasks 2-50-2, 2-25-2
Measuring cylinders of the 2nd class of accuracy with a capacity of 25, 100, 200, 1000 cm3
State standard sample of the composition of a solution of petroleum products in hexane (1 mg/cm3, the error of the certified value is not more than ±3%) - for the calibration of the analyzer		GSO 7950-2001
State standard sample of the composition of petroleum products in a solid matrix - to control the error

3.2 Reagents


Distilled water
Hexane	TU 6-09-3375-78
Hydrochloric acid, chemically pure
Sodium hydroxide, chemically pure

It is allowed to use reagents of a similar or higher qualification, manufactured according to other regulatory and technical documentation, including imported ones. Purity requirements for hexane are set out in clause 8.2. It is recommended to use hexane, special purity grade. (grade 1) produced by the company "Cryochrome".

3.3 Accessories


Glasses chemical heat-resistant with a capacity of 100, 1000 cm3
Separating funnel with a capacity of 250 cm3

Tableware preparation method is given in Appendix A. Glassware and reagents required for additional purification of extracts on an aluminum oxide column are given in Appendix B.

3.4 Preparation of solutions

3.4.1 Sodium hydroxide solution, mass fraction 5%

5 g of sodium hydroxide is dissolved in 95 ml of distilled water. The shelf life of the solution in a polyethylene vessel is 2 months.

3.4.2 Hydrochloric acid solution, 3% by volume

Pour 970 ml of water into a conical flask made of heat-resistant glass and slowly, mixing thoroughly, add 30 ml of water. of hydrochloric acid. The storage period is not limited.

3.4.3 Solution of petroleum products in hexane, mass concentration 100 mg/dm

Place 5 ml in a 50 ml volumetric flask. standard sample composition of a solution of petroleum products in hexane (nominal mass concentration 1 mg/cm), dilute with hexane to the mark and mix thoroughly.

3.4.4 Solution for calibration of the analyzer, mass concentration of NP 10 mg/dm

In a volumetric flask with a capacity of 50 cm3, 5 cm3 of a solution of oil products with a mass concentration of 100 mg / dm3 according to clause 3.4.3 is taken, diluted to the mark with hexane and mixed thoroughly.

The solution is stable for at least 3 months when stored in a refrigerated flask with a ground stopper under conditions that prevent evaporation of the solvent.

For the preparation of the calibration solution, hexane from the same batch is used as for the extraction of oil products from samples. When replacing a batch of hexane, it is necessary to check its purity (clause 8.2) and if it differs from the values obtained when checking the purity of hexane of the previous batch by more than 10%, the calibration solutions must be prepared again.

Vessels for preparing solutions should be prepared in accordance with Appendix A.

Note. If the source of sample contamination with oil products is known, it is allowed to use solutions of oil products in hexane, which is the basis of contamination, for calibrating the analyzer. The method for preparing a solution of a mass concentration of 100 mg / dm is given in Appendix B.

4 METHOD OF MEASUREMENT

The fluorimetric method for measuring the mass concentration of oil products is based on their extraction with hexane from a water sample and measuring the fluorescence intensity of the extract on a Fluorat-02 liquid analyzer.

5 SAFETY REQUIREMENTS

When measuring the mass concentration of oil products, it is necessary to comply with the safety requirements when working with chemical reagents in accordance with GOST 12.1.007-76, the electrical safety requirements when working with electrical installations in accordance with GOST 12.1.019-79 *, as well as the requirements set forth in the technical documentation for the liquid analyzer "Fluorat-02".
______________
* GOST R 12.1.019-2009 has been in force on the territory of the Russian Federation since 01/01/2011. - Database manufacturer's note.

The room must comply with the fire safety requirements in accordance with GOST 12.1.004-85 * and have fire extinguishing equipment in accordance with GOST 12.4.009-83. The content of harmful substances in the air should not exceed allowed values according to GOST 12.1.007-76. Organization of training of workers in labor safety in accordance with GOST 12.0.004-90.
______________
* On the territory of the Russian Federation, GOST 12.1.004-91 applies. - Database manufacturer's note.

6 OPERATOR QUALIFICATION REQUIREMENTS

To perform measurements and process their results, a specialist with a higher or secondary specialized chemical education or experience in a chemical laboratory, who has undergone appropriate instruction, has mastered the method in the process of training and complies with operational control standards when performing error control procedures, is allowed to perform measurements and process their results.

7 MEASUREMENT CONDITIONS

When performing measurements in the laboratory, the following conditions must be met:


Air temperature
Atmosphere pressure	84.0-106.7 kPa (630-800 mmHg);
Air humidity	no more than 80% at a temperature of 25 °C;
Mains voltage
AC frequency

8 PREPARATION FOR MEASUREMENTS

Before measurements must be taken following works: sampling, calibration of the liquid analyzer "Fluorat-02" and control of the purity of hexane.

8.1 Sampling

Water sampling is carried out in pre-prepared and dried glassware. Before use, the glassware for sampling is checked for purity, for which it is washed with hexane (at least 5 cm3), poured into the cuvette of the Fluorat-02 analyzer, and J0 is measured in the "Calibration" mode. The value obtained should not differ from the values obtained when checking the purity of hexane (clause 8.2) by more than 10%.

The volume of the sample taken is 100 cm3. The ingress of a film of oil products into the sample being taken is unacceptable!

The analysis must be performed within 3 hours after sampling, or the extraction of oil products must be carried out in accordance with clause 9. Sample hexane extract can be stored for 1 week in a stoppered flask under conditions preventing solvent evaporation.

8.2 Checking the purity of hexane

Install a cuvette with hexane into the cuvette compartment, enter the "Calibration" menu and register the value "J0". Log the received value (). A cuvette with a solution of NP mass concentration =10 mg/dm in hexane is placed in the cuvette compartment, the key is pressed and the value "J0" is recorded again. Write the received value () to the log. According to formula (1), the minimum determined mass concentration of NP in hexane (, mg/dm) is calculated, which limits the lower limit of the range of determination of NP:

The minimum determined mass concentration of NP in water, taking into account the concentration, is 10 times lower than .

Hexane is suitable for performing the determination if the obtained value of the minimum determined mass concentration of OP in water does not exceed the specified value (for example, 0.2 MPC). Otherwise, the solvent must be replaced.

Notes. 1. The main text of the methodology describes the procedure for using the Fluorat-02-2M and Fluorat-02-3M analyzers. The operating procedure on analyzers of modifications "Fluorat-02-1" and "Fluorat-02-3" is given in Appendix G.