NATIONAL STANDARD of
THE PEOPLE’S REPUBLIC OF CHINA
中华人民共和国国家标准
Integrated Water Discharge Standard
污水综合排放标准
Date of Approval : Oct. 4, 1996
Date of Enforcement: Jan. 1, 1998
Preface
The standard is the revised edition of “Integrated Wastewater Discharge Standard”(GB8978-88).
The major contents for the revision are: put forward the standard of fixed date to substitute the classification of the existing enterprise and the new construction, extension and reconstruction (NCER) enterprise in previous standard. The time divided is determined according to the implementation date of this standard. The organizations built before December 31st, 1997 are required to implement the limit in the first time phase. The organizations built after the January 1st, 1998 are required to implement the limit in the second time phase.
As for the applying scope of the standard, the principle is clear that the integrated wastewater discharge standard can not overlap with the trade discharge standard. Wastewater discharged from the paper industry, ship, ship-building industry, off-shore oil exploitation industry, dyeing & finishing of textile industry, meat processing industry, synthetic ammonia industry, iron and steel industry, space propellant, ordnance industry, phosphate fertilizer industry, caustic alkali and polyvinyl chloride industries is required to implement the corresponding national trade standards. All the other organizations discharging wastewater are required to implement this standard. Except the above-mentioned 12 trades, the following 17 issued water pollutants discharge standards are included in this revision.
Compared with the previous standard, the standard limits in the first time phase are kept on the same level of the NCER enterprises of the previous standard. In order to control the characteristic pollutants and other poisonous and harmful pollutants in the water pollutants discharge standards on the 17 special trades that have been included in this revision, 10 items for control are added. As for the standard limits of the second time phase, 40 items for control are added. The maximum allowable discharge concentration of the items such as COD, BOD5 is restricted properly.
The standard substitutes GB8978-88 and the following standards since the enforcement date of this standard.
GBJ 48-83 Discharge Standard for Sewage from Hospital (trial)
GB3545-83 Discharge Standard for Water Pollutants from Beet Processing Industry
GB3546-83 Discharge Standard for Water Pollutants from Sugar-cane Processing Industry
GB3547-83 Discharge Standard for Pollutants from Synthetic Fatty Acid Industry
GB3548-83 Discharge Standard for Pollutants from Synthetic Detergent Industry
GB3549-83 Effluent Standard for Pollutants from Leather Industry
GB3550-83 Discharge Standard for Water Pollutants from Petroleum Exploitation Industry
GB3551-83 Discharge Standard for Water Pollutants from Petroleum Refining Industry
GB3553-83 Discharge Standard for Water Pollutants from Cinefilm Processing
GB4280-84 Discharge Standard for Pollutants from Chromate Salt Industry
GB4281-84 Discharge Standard for Water Pollutants from Petrochemical Industry
GB4282-84 Discharge Standard for Pollutants from Sulfuric Acid Industry
GB4283-84 Discharge Standard for Pollutants from Phosphor Industry
GB4912-85 Effluent Standard for Pollutants from Light Metal Industry
GB4913-85 Effluent Standard for Pollutants from Heavy Non-ferrous Metal Industry
GB4916-85 Emission Standard for Pollutants from Asphalt Industry
GB5469-85 Discharge Standard for Pollutants from Scrubbing Goods Trains
Appendixes A, B, C and D are all the appendixes of this standard.
This standard was issued in 1973 for the first time. It was first revised in 1988.
This standard was proposed by the Department of Science, Technology & Standard, National Environmental Protection Administration (NEPA).
NEPA is in charge of the explanation of this standard.
NATIONAL STANDARD OF THE PEOPLE’S REPUBLIC OF CHINA
Integrated Wastewater Discharge Standard
GB8978-1996
Substitution for GB8978-88
This standard is hereby enacted to implement “Environmental Protection Law of the People’s Republic of China”, “Law of the People’s Republic of China on the Prevention and Control of Water Pollution”, “Law of Marine Environmental Protection of the People’s Republic of China”, for controlling the water pollution, keeping the water quality of surface water bodies (rivers, lakes, canals, channels, reservoirs and oceans) and the underground water bodies in good condition, safeguarding human health, preserving the ecological balance and promoting the development of national economy and construction in urban and rural areas.
1. The Content of Theme and Applying Scope
1.1 The Content of Theme
The standard stipulates, in accordance with the time phase for enterprise being built and destination of wastewater, the maximum allowable discharge concentration of 69 kinds of water pollutants and the maximum allowable discharge capacity for some trades.
1.2 Applying Scope
This standard is applicable for the discharge management of water pollutants from the existing enterprises, the environmental impact assessment and the design of environment protection facilities of construction projects, the acceptance of construction projects upon completion and the discharge management after they are put into production.
In accordance with the principle that the national integrated wastewater discharge standard can’t overlap with national trade discharge standard, the paper industry should implement “Discharge Standard of Water Pollutants from Paper industry” (GB3544-92); the ship should implement “Discharge Standard for Pollutants from Ship”(GB3552-83); the ship industry should implement “Emission Standard for Pollutants from Ship Building Industry” (GB4286-84); the off-shore petroleum exploitation industry should implement “Discharge Standard for Oil-bearing Wastewater from Off-shore Petroleum Exploitation Industry” (GB4944-85); the dyeing and finishing of textile industry should implement “Discharge Standard of water Pollutants from Dyeing and Finishing Textile Industry”(GB4287-92); the meat processing industry should implement “Discharge Standard of Water Pollutants from Meat Processing Industry”(GB13457-92); the synthetic ammonia industry should implement “Discharge Standard of Water Pollutants from Synthetic Ammonia Industry”(GB12458-92); the iron and steel industry should implement “Discharge Standard of Water Pollutants from Iron & Steel Industry”(GB13456-92); the space propellant should implement “Discharge Standard of Water Pollutants from Space Propellant”(GB14374-93); the weaponry industry should implement “Discharge Standard of Water Pollutants from Weaponry Industry” (GB14470.1~GB14470.3-93 & GB4274~4279-84), the phosphate fertilizer industry should implement “Discharge Standard of Water Pollutants from Phosphate Fertilizer Industry”(GB15580-95); the caustic alkali and polyvinyl chloride industry should implement “Discharge Standard of Water Pollutants from Caustic Soda and Polyvinyl Chloride Industry”(GB15581-95). The discharge of all the other water pollutants should implement this standard.
1.3 After the standard is issued, the trades are added by the new national trade water pollutants discharge standard, are required to implement the corresponding national trade water pollutants discharge standard according to their applying scope, but aren’t required to implement this standard again.
2. Cited Standard
The articles of following standards become the articles of this standard when they are cited in this standard. The following standards are valid when this standard is published. Because all standards will be revised, all parties concerned with the application of this standard shall investigate the possibility of applying the latest revision of the following standards.
GB3097-82 Marine Water Quality Standard
GB3838-88 Environmental Quality Standard for Surface Water
GB8703-88 Regulation of Radiation Protection
3. Definition
3.1 Wastewater
Means the general term of the water discharged from the production and domestic activities.
3.2 Discharge capacity
Means discharge capacity of water directly used for the process production, which excludes the indirect cooling water, the water discharged from the boiler and the power station within plant.
3.3 All Enterprises Discharging Pollutants (AEDP)
Means all of the enterprise discharging pollutants covered by the applying scope of this standard.
3.4 Other Enterprises Discharging Pollutants (OEDP)
Means, in a certain control item, all the enterprises discharging pollutants except those trades that are listed in this item.
4. Technical Contents
4.1 Classification of the Discharging Standard
4.1.1 Class A is the standard that is required to implement for the wastewater discharged into the class C water area (not including the designated protection areas and swimming zones) in GB3838 and the class two sea area in GB3097.
4.1.2 Class B is the standard that is required to implement for the wastewater discharged into the class D and class E water area in GB3838 and the class three sea area in GB3097.
4.1.3 Class C is the standard that is required to implement for the wastewater discharged into the urban drainage system equipped with the secondary wastewater treatment plant.
4.1.4 In accordance with the function and requirement of the water area receiving the wastewater, stipulation 4.1.1 and 4.1.2 shall be implemented respectively for the wastewater discharged into the urban drainage system without secondary treatment plant.
4.1.5 The construction of the new wastewater outlets in class A and class B water areas and the designated protection area and in class C water area defined by GB3838 as well as in the class one sea area defined by GB3097 is forbidden. The control for total pollutants should be carried out for the existing wastewater outlets according to the requirements of the water body function to guarantee the water quality of the receiving water area to satisfy the water quality for designated use.
4.2 Standard Value
4.2.1 This standard classifies the discharge pollutants into two categories in accordance with their property and the controlling method.
4.2.1.1 Pollutants of the first category: The samples shall all be taken at the outlet of the workshop or the workshop treatment facility, regardless of the trades they belong to, the wastewater discharge methods and the function of the receiving water body. Their maximum allowable discharge concentrations must meet the requirements of this standard (The tailings dam outlet of the mining can’t be regarded as the workshop outlet).
4.2.1.2 Pollutants of the second category: The samples shall be taken at the discharging outlet of the enterprise, their maximum allowable discharge concentrations must meet the requirements of this standard.
4.2.2 In accordance with the fixed date, this standard stipulates the maximum allowable discharge concentrations of the pollutants of the first and the second categories and the maximum allowable discharge capacities for some trades as follows:
4.2.2.1 The enterprises (including reconstruction and extension) built before December 31, 199 are required to implement simultaneously the stipulations in table 1, table 2 and table 3 for the discharge of water pollutants.
4.2.2.2 The enterprises (including reconstruction and extension) built after January 1, 1998, are required to implement simultaneously the stipulations in table 1, table 4 and table 5 for the discharge of water pollutants.
4.2.2.3 The building date of enterprise (including reconstruction and extension) is determined according the approval date of the environmental impact assessment report.
4.3 Other Stipulations
4.3.1 When a outlet discharges two or more than two kinds of different wastewater and they are required to implement different discharge standard, the discharge standard of the mixed wastewater should be calculated according to appendix A.
4.3.2 The maximum allowable discharge load capacity of the industry wastewater pollutants should be calculated according to appendix B.
4.3.3 The yearly total maximum allowable discharge amount of the pollutants should be calculated according to appendix C.
4.3.4 Enterprises discharging radioactive wastewater should meet the requirements of GB8703-88 “ Regulations for Radiation Protection” as well as this standard.
Table 1 Maximum Allowable Discharge Concentration for Pollutants of the First Category
Unit: mg/L
|
No. |
Pollutant |
Maximum Allowable Discharge Concentration |
|
1 |
Total mercury |
0.05 |
|
2 |
Mercury alkyl |
Undetectable |
|
3 |
Total cadmium |
0.1 |
|
4 |
Total chromium |
1.5 |
|
5 |
Chromium(VI) |
0.5 |
|
6 |
Total arsenic |
0.5 |
|
7 |
Total lead |
1.0 |
|
8 |
Total nickel |
1.0 |
|
9 |
Benzo(a)-pyrene |
0.00003 |
|
10 |
Total beryllium |
0.005 |
|
11 |
Total silver |
0.5 |
|
12 |
Total αradiation |
1Bq/L |
|
13 |
Total βradiation |
10Bq/ L |
Table 2 Maximum Allowable Discharge Concentration for Pollutants of the Second Category
(Enterprise built before December 31,1997)
Unit: mg/L
|
No |
Pollutant |
Applying Scope |
Class A |
Class B |
Class C |
|
1. |
pH |
All enterprises discharging pollutants (AEDP) |
6~9 |
6~9 |
6~9 |
|
2 |
Color (dilution factor) |
Dye industry |
50 |
180 |
-- |
|
Other enterprises discharging pollutants (OEDP) |
50 |
80 |
-- |
|
3 |
SS |
Mining, coal separation, ore dressing |
100 |
300 |
-- |
|
Veined gold ore dressing |
100 |
500 |
-- |
|
Remote zone alluvial ore dressing |
100 |
800 |
-- |
|
Urban secondary sewage treatment plant |
20 |
30 |
-- |
|
OEDP |
70 |
200 |
400 |
|
4 |
BOD5 |
Sugar-cane processing, ramie degumming, wet process for fiber board industry |
30 |
100 |
600 |
|
Beet sugar processing, alcohol, monosodium glutamate, leather, chemical pulp industry |
30 |
150 |
600 |
|
Urban secondary sewage treatment plant |
20 |
30 |
-- |
|
OEDP |
30 |
60 |
300 |
|
5 |
COD |
Beet sugar manufacturing, coking, synthetic fatty acid, wet process for fiber board, dye, wool scouring, and organ-phosphorous pesticide industry |
100 |
200 |
1000 |
|
Monosodium glutamate, alcohol, medical raw material pharmaceuticals, biotic pharmaceuticals
production, ramie degumming, leather, chemical pulp industry |
100 |
300 |
1000 |
|
Petrochemical industry (including petroleum refining) |
100 |
150 |
500 |
|
Urban secondary sewage treatment plant |
60 |
120 |
-- |
|
OEDP |
100 |
150 |
500 |
|
6 |
Petroleum |
AEDP |
10 |
10 |
30 |
|
7 |
Animal and plant oil |
AEDP |
20 |
20 |
100 |
|
8 |
Volatile phenol |
AEDP |
0.5 |
0.5 |
2.0 |
|
9 |
Total cyanide |
Film developing (ferric cyanide) |
0.5 |
5.0 |
5.0 |
|
OEDP |
0.5 |
0.5 |
1.0 |
|
10 |
Sulfide |
AEDP |
1.0 |
1.0 |
2.0 |
|
11 |
Ammonia nitrogen (NH3-N) |
Medical raw material pharmaceuticals, dye and petrochemical industry |
15 |
50 |
-- |
|
OEDP |
15 |
25 |
-- |
|
12 |
Fluoride |
Yellow phosphor industry |
10 |
20 |
20 |
|
Low fluorine area (the fluorine concentration in water is less than 0.5 mg/L) |
10 |
20 |
30 |
|
OEDP |
10 |
10 |
20 |
|
13 |
Phosphate (as P) |
AEDP |
0.5 |
1.0 |
-- |
|
14 |
Formaldehyde |
AEDP |
1.0 |
2.0 |
5.0 |
|
15 |
Aniline compounds |
AEDP |
1.0 |
2.0 |
5.0 |
|
16 |
Nitrobenzene compounds |
AEDP |
2.0 |
3.0 |
5.0 |
|
17 |
Anionic surfactants (LAS) |
Synthetic detergent industry |
5.0 |
15 |
20 |
|
OEDP |
5.0 |
10 |
20 |
|
18 |
Total copper |
AEDP |
0.5 |
1.0 |
2.0 |
|
19 |
Total zinc |
AEDP |
2.0 |
5.0 |
5.0 |
|
20 |
Total manganese |
Synthetic fatty acid industry |
2.0 |
5.0 |
5.0 |
|
OEDP |
2.0 |
2.0 |
5.0 |
|
21 |
Color developer |
Film developing |
2.0 |
3.0 |
5.0 |
|
22 |
Developer and total oxide |
Film developing |
3.0 |
6.0 |
6.0 |
|
23 |
Phosphorus |
AEDP |
0.1 |
0.3 |
0.3 |
|
24 |
Organ-phosphorous pesticide (as P) |
AEDP |
un detectable |
0.5 |
0.5 |
|
25 |
Fecal coliform index (individual/ L) |
Wastewater containing the pathogen from the hospital*, the veterinary hospital and the medical institution |
500/L |
1000/L |
5000/L |
|
Wastewater from the contagious hospital and the tuberculosis hospital |
100/L |
500/L |
1000/L |
|
26 |
Total residual chlorine (wastewater from the hospital with chlorine disinfection) |
Wastewater containing the pathogen from the hospital*, the veterinary hospital and the medical institution |
<0.5** |
>3 (contact time ≥1h) |
>2 (contact time ≥1h) |
|
Wastewater from the contagious hospital and the tuberculosis hospital |
<0.5** |
>6.5(contact time ≥1.5h) |
>5(contact time ≥1.5h) |
|
*: Means hospital with more than 50 beds.
**: Means the standard shall be satisfied with de-chlorination treatment after chlorine disinfection. |
Table 3 Maximum Allowable Water Discharge for Some Trades
(Enterprise built before December 31, 1997)
|
No. |
Trade |
Maximum Allowable Water Discharge Quantity or Minimum Allowable Water Reuse Rate |
|
1 |
Mining industry |
Nonferrous metal ore industry |
Water reuse rate :75% |
|
Mining, ore dressing, coal separation, etc., of other mining industries |
Water reuse rate :90% (coal separation) |
|
Veined gold mining ore dressing |
Gravity separation |
16.0m3/t (ore) |
|
Flotation |
9.0m3/t (ore) |
|
Cyanidation |
8.0m3/t (ore) |
|
Carbon adsorption |
8.0m3/t (ore) |
|
2 |
Coking enterprise (gas works) |
1.2m3/t (coke) |
|
3 |
Nonferrous metal smelting and metal processing |
Water reuse rate: 80% |
|
4 |
Petroleum refinery industry (excluding refinery plant discharging wastewater directly)
Processing classification:
A. Refinery for fuel oil
B. Refinery for fuel oil and lubricants
C. Refinery producing the fuel oil, lubricants and petroleum chemicals (including refinery for crude oil, shale oil, petroleum additive) |
A |
>5,000kt, 1.0 m3/t(crude oil)
2500~5000kt, 1.2 m3/t(crude oil)
<2500kt, 1.5 m3/t(crude oil)
|
|
B |
>5,000kt, 1.5 m3/t(crude oil)
2500~5000kt, 2.0 m3/t(crude oil)
<2500kt, 2.0 m3/t(crude oil)
|
|
C |
>5,000kt, 2.0 m3/t(crude oil)
2500~5000kt, 2.5 m3/t(crude oil)
<2500kt, 2.5 m3/t(crude oil)
|
|
5 |
Synthetic detergent industry |
Chlorination process for alkylbenzenes (ABS) production |
200.0 m3/t(alkyl benzene) |
|
Cracking process for ABS production |
70.0 m3/t(alkyl benzene) |
|
ABS for synthetic detergent production |
10.0 m3/t(product) |
|
6 |
Synthetic fatty acid industry |
200.0 m3/t(product) |
|
7 |
Fiber board industry with Wet process manufacturing |
30.0 m3/t(board) |
|
8 |
Sugar processing |
Sugar-cane manufacturing |
10.0 m3/t(cane) |
|
Beet sugar manufacturing |
4.0 m3/t(beet) |
|
9 |
Leather industry |
Wet and salt hogskin |
60.0 m3/t(raw hide) |
|
Dry oxhide |
100.0 m3/t(raw hide) |
|
Dry sheep skin |
150.0 m3/t(raw hide) |
|
10 |
Fermentation, brewery industry |
Alcohol industry |
Raw material: maize |
100.0 m3/t(alcohol) |
|
Raw material: potato |
80.0 m3/t(alcohol) |
|
Raw material: molasses |
70.0 m3/t(alcohol) |
|
Monosodium glutamate industry |
600.0 m3/t(monosodium glutamate) |
|
Brewery (excluding malt affluent) |
16.0 m3/t(beer) |
|
11 |
Chromic salt industry |
5.0 m3/(product) |
|
12 |
Sulfuric acid industry (water washing process) |
15.0 m3/t(sulfuric acid) |
|
13 |
Ramie degumming industry |
500 m3/t(raw ramie) or 750 m3/t(dry fine ramie) |
|
14 |
Chemical pulp |
Natural color: 150 m3/(pulp) |
|
Bleaching : 240 m3/(pulp) |
|
15 |
Rayon fiber industry (pure fiber) |
Short fiber (cotton type medium and long fiber, wool type medium and long fiber) |
300 m3/(fibre) |
|
Long fiber |
800 m3/(fibre) |
|
16 |
Railway freight train washing |
5.0 m3/(freight train) |
|
17 |
Film developing |
5 m3/1000m (35mm film) |
|
18 |
Petroleum asphalt industry |
Water reuse rate of cooling tank: 95% |
|
|
|
|
|
|
|
|
Table 4 Maximum Allowable Discharge Concentration for Pollutants of Second Category
(Enterprise built after January 1st, 1998)
Unit: mg/L
|
No |
Pollutants |
Applying Scope |
Class A |
Class B |
Class C |
|
1. |
pH |
AEDP |
6~9 |
6~9 |
6~9 |
|
2 |
Color (dilution factor) |
AEDP |
50 |
80 |
|
|
3 |
SS |
Mining, coal separation, ore dressing industry |
70 |
300 |
|
|
Veined gold ore dressing |
70 |
400 |
|
|
Remote zone alluvial ore dressing |
70 |
800 |
|
|
Urban secondary sewage treatment plant |
20 |
30 |
|
|
OEDP |
70 |
150 |
400 |
|
4 |
BOD5 |
Sugar-cane processing, ramie degumming, fiber board with wet process industry, wool scouring industry |
20 |
60 |
600 |
|
Beet sugar manufacturing, alcohol, monosodium glutamate, leather, chemical pulp industry |
20 |
100 |
600 |
|
Urban secondary sewage treatment plant |
20 |
30 |
-- |
|
OEDP |
20 |
30 |
300 |
|
5 |
COD |
Beet sugar manufacturing, synthetic fatty acid, fiber board with wet process, dye , wool scouring and organ-phosphorous pesticide industry |
100 |
200 |
1000 |
|
monosodium glutamate, alcohol, medical raw material pharmaceuticals, biotic pharmaceuticals, ramie degumming, leather, chemical pulp industry |
100 |
300 |
1000 |
|
Petrochemical industry (including petroleum refining) |
60 |
120 |
500 |
|
Urban secondary sewage treatment plant |
60 |
120 |
-- |
|
OEDP |
100 |
150 |
500 |
|
6 |
Petroleum |
AEDP |
5 |
10 |
20 |
|
7 |
Animal and plant Oil |
AEDP |
10 |
15 |
100 |
|
8 |
Volatile phenol |
AEDP |
0.5 |
0.5 |
2.0 |
|
9 |
Total cyanide |
AEDP |
0.5 |
0.5 |
1.0 |
|
10 |
Sulfide |
AEDP |
1.0 |
1.0 |
1.0 |
|
11 |
Ammoniac nitrogen (NH3-N) |
Medical raw material pharmaceuticals, dye and petrochemical industry |
15 |
50 |
-- |
|
OEDP |
15 |
25 |
-- |
|
12 |
Fluoride |
Yellow phosphor industry |
10 |
15 |
20 |
|
Low fluorine area (the fluorine concentration in water is less than 0.5 mg/L) |
10 |
20 |
30 |
|
OEDP |
10 |
10 |
20 |
|
13 |
Phosphate (as P) |
AEDP |
0.5 |
1.0 |
-- |
|
14 |
Formaldehyde |
AEDP |
1.0 |
2.0 |
5.0 |
|
15 |
Aniline compounds |
AEDP |
1.0 |
2.0 |
5.0 |
|
16 |
Nitrobenzene compounds |
AEDP |
2.0 |
3.0 |
5.0 |
|
17 |
Anionic surfactants (LAS) |
AEDP |
5.0 |
10 |
20 |
|
18 |
Total copper |
AEDP |
0.5 |
1.0 |
2.0 |
|
19 |
Total zinc |
AEDP |
2.0 |
5.0 |
5.0 |
|
20 |
Total manganese |
Synthetic fatty acid industry |
2.0 |
5.0 |
5.0 |
|
OEDP |
2.0 |
2.0 |
5.0 |
|
21 |
Color developer |
Film developing |
1.0 |
2.0 |
3.0 |
|
22 |
Developer and total oxide |
Film developing |
3.0 |
3.0 |
6.0 |
|
23 |
Phosphorus |
AEDP |
0.1 |
0.3 |
0.3 |
|
24 |
Organ-phosphorous pesticide (as P) |
AEDP |
Undetectable |
0.5 |
0.5 |
|
25 |
Rogor
|
AEDP |
Undetectable |
1.0 |
2.0 |
|
26 |
Parathion |
AEDP |
Undetectable |
1.0 |
2.0 |
|
27 |
Methyl parathion |
AEDP |
Undetectable |
1.0 |
2.0 |
|
28 |
Malathion |
AEDP |
Undetectable |
5.0 |
10 |
|
29 |
Pentachlorophenol and sodium pentachlorophenate |
AEDP |
5.0 |
8.0 |
10 |
|
30 |
AOX (calculated as Cl) |
AEDP |
1.0 |
5.0 |
8.0 |
|
31 |
Trichloromethane |
AEDP |
0.3 |
0.6 |
1.0 |
|
32 |
Carbon tetrachloriode |
AEDP |
0.03 |
0.06 |
0.5 |
|
33 |
Trichloroethylene |
AEDP |
0.3 |
0.6 |
1.0 |
|
34 |
Tetrafluoroethylene |
AEDP |
0.1 |
0.2 |
0.5 |
|
35 |
Benzene |
AEDP |
0.1 |
0.2 |
0.5 |
|
36 |
Toluene |
AEDP |
0.1 |
0.2 |
0.5 |
|
37 |
Ethyl-benzene |
AEDP |
0.4 |
0.6 |
1.0 |
|
38 |
o-xylene |
AEDP |
0.4 |
0.6 |
1.0 |
|
39 |
p- xylene |
AEDP |
0.4 |
0.6 |
1.0 |
|
40 |
m- xylene |
AEDP |
0.4 |
0.6 |
1.0 |
|
41 |
Chlorobenzene |
AEDP |
0.2 |
0.4 |
1.0 |
|
42 |
o-dichlorobenzene |
AEDP |
0.4 |
0.6 |
1.0 |
|
43 |
p-dichlorobenzene |
AEDP |
0.4 |
0.6 |
1.0 |
|
44 |
p-nitrochlorobenzene |
AEDP |
0.5 |
1.0 |
5.0 |
|
45 |
2.4-dinitro-chlorobenzene |
AEDP |
0.5 |
1.0 |
5.0 |
|
46 |
Phenol |
AEDP |
0.3 |
0.4 |
1.0 |
|
47 |
m-cresol |
AEDP |
0.1 |
0.2 |
0.5 |
|
48 |
2,4-dichlorophenol |
AEDP |
0.6 |
0.8 |
1.0 |
|
49 |
2,4,6-trichlorophenol |
AEDP |
0.6 |
0.8 |
1.0 |
|
50 |
Dibutyl phthalate |
AEDP |
0.2 |
0.4 |
2.0 |
|
51 |
Di-octyl phthalate |
AEDP |
0.3 |
0.6 |
2.0 |
|
52 |
Acrylonitrile |
AEDP |
2.0 |
5.0 |
5.0 |
|
53 |
Total selenium |
AEDP |
0.1 |
0.2 |
0.5 |
|
54 |
Fecal coliform index (individual/L) |
Wastewater containing the pathogen from the hospital*, the veterinary hospital and medical institution |
500/L
|
1000/L
|
5000/L
|
|
Wastewater from the contagious hospital and the tuberculosis hospital |
100/L |
500/L |
1000/L |
|
55 |
Total residual chlorine (wastewater from the hospital with chlorine disinfection) |
Wastewater containing the pathogen from the hospital*, the veterinary hospital and medical institution |
<0.5**
|
>3 (contact time ≥1h)
|
>2 (contact time ≥1h)
|
|
Wastewater from the contagious hospital and the tuberculosis hospital |
<0.5** |
>6.5(contact time ≥1.5h) |
>5(contact time ≥1.5h) |
|
56 |
Total organic carbon |
Synthetic fatty acid industry |
20 |
40 |
|
|
Ramie degumming industry |
20 |
60 |
|
|
OEDP |
20 |
30 |
|
|
Note: Other enterprises discharging pollutants means all the wastewater discharging enterprises other than those that are already listed in the controlling item.
*: Means hospital with more than 50 beds.
**: Means the standard shall be satisfied with de-chlorination treatment after chlorine disinfection. |
Table 5 Maximum Allowable Water Discharge Quantity for Some Trades
(Enterprises built after January 1, 1998)
|
No. |
Trade |
Maximum Allowable Wastewater Discharge Quantity or Minimum Allowable Water Reuse Rate |
|
1 |
Mining industry |
Nonferrous metal ore industry |
Water reuse rate :75% |
|
Mining, ore dressing, coal separation, etc., of other mining industries |
Water reuse rate :90% (coal separation) |
|
Veined gold mining ore dressing |
Gravity separation |
16.0m3/t (rock) |
|
Flotation |
9.0m3/t (rock) |
|
Cyanidation |
8.0m3/t (rock) |
|
Carbon adsorption |
8.0m3/t (rock) |
|
2 |
Coking enterprise (gas works) |
1.2m3/t (coke) |
|
3 |
Nonferrous metal smelting and metal processing |
Water reuse rate: 80% |
|
4 |
Petroleum refinery industry (excluding refinery plant discharging wastewater directly)
Processing classification:
A. Refinery for fuel oil
B. Refinery for fuel oil and lubricants
C. Refinery producing the fuel oil, lubricants and petroleum chemicals (including refinery for crude oil, shale oil, petroleum additive) |
A |
>5,000kt, 1.0 m3/t(crude oil)
2500~5000kt, 1.2 m3/t(crude oil)
<2500kt, 1.5 m3/t(crude oil)
|
|
B |
>5,000kt, 1.5 m3/t(crude oil)
2500~5000kt, 2.0 m3/t(crude oil)
<2500kt, 2.0 m3/t(crude oil)
|
|
C |
>5,000kt, 2.0 m3/t(crude oil)
2500~5000kt, 2.5 m3/t(crude oil)
<2500kt, 2.5 m3/t(crude oil)
|
|
5 |
Synthetic detergent industry |
Chlorination process for alkylbenzenes (ABS) production |
200.0 m3/t(alkyl benzene) |
|
Cracking process for ABS production |
70.0 m3/t(alkyl benzene) |
|
ABS for synthetic detergent production |
10.0 m3/t(product) |
|
6 |
Synthetic fatty acid industry |
200.0 m3/t(product) |
|
7 |
Fiber board industry with Wet process manufacturing |
30.0 m3/t(board) |
|
8 |
Sugar manufacturing industry |
Sugar-cane manufacturing |
10.0 m3/t(cane) |
|
Beet sugar manufacturing |
4.0 m3/t(beet) |
|
9 |
Leather industry |
Wet and salt hogskin |
60.0 m3/t(raw leather) |
|
Dry oxhide |
100.0 m3/t(raw leather) |
|
Dry sheep skin |
150.0 m3/t(raw leather) |
|
10 |
Fermentation, brewery industry |
Alcohol industry |
Raw material: maize |
100.0 m3/t(alcohol) |
|
Raw material: potato |
80.0 m3/t(alcohol) |
|
Raw material: molasses |
70.0 m3/t(alcohol) |
|
Monosodium glutamate |
600.0 m3/t(monosodium glutamate) |
|
Brewery (excluding the malt effluent) |
16.0 m3/t(beer) |
|
11 |
Chromic salt industry |
5.0 m3/t(product) |
|
12 |
Sulfuric acid (water washing process) |
15.0 m3/t(sulfuric acid) |
|
13 |
Ramie degumming industry |
500 m3/t(raw ramie) or 750 m3/t(dry fine ramie) |
|
14 |
Rayon fiber industry (pure fiber) |
Short fiber (cotton type medium and long fiber, wool type medium and long fiber) |
300 m3/(fiber) |
|
Long fiber |
800 m3/(fiber) |
|
15 |
Chemical pulp |
Original color: 150 m3/(pulp), bleached: 240 m3/(pulp) |
|
16 |
Pharmaceutical production industry, medical raw material pharmaceuticals |
Penicillin |
4700 m3/t (penicillin) |
|
Streptomycin |
1450 m3/t (streptomycin) |
|
Riomistin |
1300 m3/t (riomistin) |
|
Neotetrine |
1900 m3/t (neotetrine) |
|
Lincomycin |
9200 m3/t (lincomycin) |
|
Aureomycin |
3000 m3/t (aureomycin) |
|
Gentamicin |
20400 m3/t (gentamicin) |
|
Vitamin C |
1200 m3/t (Vitamin C) |
|
Chlormycetin |
2700 m3/t (chlormycetin) |
|
Sulfamethoxazole |
2000 m3/t (sulfamethoxazole) |
|
Vitamin B1 |
3400 m3/t (Vitamin B1) |
|
Analgin |
180 m3 /t (analgin) |
|
Phenacetine |
750 m3/t (phenacetine) |
|
Furaxone |
2400 m3/t (furaxone) |
|
Caffeine |
1200 m3/t (caffeine) |
|
17 |
Organ-phosphorus pesticide industry |
Rogor ** |
700 m3/t (product) |
|
Parathion-methyl (water phase method) * |
300m3/t (product) |
|
DNTP(P2S5 process) |
500 m3/t (product) |
|
DNTP (PSCL3 process) |
550 m3/t (product) |
|
DDV (trichlorfon method) |
200 m3/t (product) |
|
Trichlorfon |
40 m3/t(product) (not including the wastewater from the trichloroacetaldehyde production) |
|
malathion |
700 m3/t(product) |
|
18 |
Herbicide industry |
Nitrofen |
5 m3/t(product) |
|
Sodium pentachlorophenate |
2 m3/t(product) |
|
Pentachloro-phenol |
4 m3/t(product) |
|
Mecoprop (MCP) |
14 m3/t(product) |
|
2,4-D |
4 m3/t(product) |
|
Butachlor |
4.5 m3/t(product) |
|
Chlorotoluron (reduced by iron powder ) |
2 m3/t(product) |
|
Chlorotoluron (reduced by Na2S) |
3 m3/t(product) |
|
19 |
Thermal power generation industry |
3.5 m3/(MW·h) |
|
20 |
Railway freight train washing |
5.0 m3/freight train |
|
21 |
Film developing |
5 m3/1000m(35mm film) |
|
22 |
Petroleum asphalt industry |
Water recycling ration of cooling water: 95% |
|
Note: *: The product is calculated according to 100% (concentration).
**: Excluding the wastewater from raw materials production such as P2S5, PSCl3, PCl3. |
|
|
|
|
|
|
|
|
5. Monitoring
5.1 Sampling Points
The sampling points shall be at the locations stipulated for the discharge outlets of the first and the second categories of pollutants in 4.2.1.1 and 4.2.1.2. The discharge outlet shall be furnished with outlet signs, wastewater metering device and wastewater proportional sampling device.
5.2 Sampling Frequency
The monitoring frequency of the industry wastewater is determined by the production cycle. The sampling is conducted every 2 hours if the production cycle is less than 8 hours. If the production cycle is longer than 8 hours, the sampling is done every 4 hours. The frequency of sampling for other kinds of wastewater shall not be less than twice every 24 hours. The maximum allowable discharge concentration is calculated based on the daily average.
5.3 Discharge Quantity
It is controlled by the maximum allowable discharge quantity or the minimum allowable reuse rate on the monthly average.
5.4 Statistics
The consumption of raw materials and product output in the enterprise should be obtained from the legal monthly report or the annual report.
5.5 Measuring Method
The measuring methods are listed in table 6.
Table 6 Measuring Method
|
No |
Pollutant |
Measuring method |
Source of method |
|
1. |
Total mercury |
Cold atomic absorption photometric method |
GB7468-87 |
|
2 |
Mercury alkyl |
Gas chromatograhpy |
GB/T14204-93 |
|
3 |
Total cadmium |
Atomic adsorption spectrophotometry |
GB7475-87 |
|
4 |
Total chromium |
Potassium permanganate oxidization 1,5 diphenylcarbohydrazide spectrophotometry |
GB7466-87 |
|
5 |
Chromium (VI) |
1,5 diphenylcarbohydrazide spectrophotomety |
GB7467-87 |
|
6 |
Total arsenic |
Silver diethyldithiocarbamate spectrophotometry |
GB7485-87 |
|
7 |
Total lead |
Atomic absorption spectrophotometry |
GB7475-87 |
|
8 |
Total nickel |
Flame atomic absorption spectrophotometry
Dimethylglyoxime spectrophotometry |
GB11912-89
GB19910-89 |
|
9 |
Benzo(a)-pyrene |
Acetylated paper chromatography with fluorescence spectrophotometry |
GB11895-89
|
|
10 |
Total beryllium |
Active carbon absorption- chrome azurols spectrophotometry |
1) |
|
11 |
Total silver |
Flame atomic absorption spectrophotometry |
GB11907-89 |
|
12 |
Total α |
Physical method |
2) |
|
13 |
Total β |
Physical method |
2) |
|
14 |
pH |
Glass electrode method |
GB6920-86 |
|
15 |
Color |
Dilution factor method |
GB11903-89 |
|
16 |
SS |
Gravimetric method |
GB11901-89 |
|
17 |
BOD5 |
Dilution and inoculation method dichromate UV spectrophotometry |
GB7488-87
To be issued |
|
18 |
COD |
Dichromate method |
GB11914-89 |
|
19 |
Petroleum |
Infrared photometric method |
GB/T16488-1996 |
|
20 |
Animal and plant oil |
Infrared photometric method |
GB/T16488-1996 |
|
21 |
Volatile phenol |
After distillation by means of 4-AAP spectrophotometry |
GB7490-87 |
|
22 |
Total cyanide |
Silver nitrate titration method |
GB7486-87 |
|
23 |
Sulfide |
Methylene blue spectrophotometry |
GB/T16489-1996 |
|
24 |
Ammonia nitrogen |
Nessler’s reagent colorimetry Distillation and titration method |
GB7478-87
GB7479-87 |
|
25 |
Fluoride |
Ionic selection electrode method |
GB7484-87 |
|
26 |
Phosphate |
Molybdenum blue colorimetry |
1) |
|
27 |
Formaldehyde |
Acetylacetone spectrophotometry |
GB13197-91 |
|
28 |
Aniline compounds |
Spectrophotometry with N-(1-naphyl) ethylenediamine |
GB11889-89 |
|
29 |
Nitrobenzene |
Reduction–azo colorimetric method or spectrophotometry |
1) |
|
30 |
Anionic surfactants |
Methylene blue spectrophotmetry |
GB7494-87 |
|
31 |
Total copper |
Atomic absorption spectrometry Sodium diethyldithiocarbamate spectrophotometry |
GB7475-87
GB7474-87 |
|
32 |
Total zinc |
Atomic absorption spectrophotometry
Spectrophotometry with dithizone |
GB7475-87
GB7472-87 |
|
33 |
Total manganese |
Flame atomic absorption spectrophotometry
Potassium periodate spectrophotometry |
GB11911-89
GB11906-89 |
|
34 |
Color developer |
169 color formation reagent method |
3) |
|
35 |
Developer and total oxide |
Iodine-starch colorimetric method |
3) |
|
36 |
Phosphorus |
Phosphorus molybdenum-blue colorimetric method |
3) |
|
37 |
Organ-phosphorus pesticide (as P) |
Determination of organic phosphorus pesticide |
GB13192-91 |
|
38 |
Rogor |
Gas chromatography |
GB13192-91 |
|
39 |
Parathion |
Gas chromatography |
GB13192-91 |
|
40 |
Methyl parathion |
Gas chromatography |
GB13192-91 |
|
41 |
Malathion |
Gas chromatography |
GB13192-91 |
|
42 |
Pentachlorophenol and sodium pentachlorophenate (as pentachlorophenol) |
Gas chromatography
Safranine-T spectrophotometry |
GB8972-88
GB9803-88 |
|
43 |
AOX (as Cl) |
Micro-coulometric method |
GB/T15959-95 |
|
44 |
Trichloromethane |
Gas chromatography |
To be issued |
|
45 |
Carbontetrachloride |
Gas chromatography |
To be issued |
|
46 |
Trichloroethylene |
Gas chromatography |
To be issued |
|
47 |
Tetrachloroethylene |
Gas chromatography |
To be issued |
|
48 |
Benzene |
Gas chromatography |
GB11890-89 |
|
49 |
Toluene |
Gas chromatography |
GB11890-89 |
|
50 |
Ethyl-benzene |
Gas chromatography |
GB11890-89 |
|
51 |
o-xylene |
Gas chromatography |
GB11890-89 |
|
52 |
p- xylene |
Gas chromatography |
GB11890-89 |
|
53 |
m- xylene |
Gas chromatography |
GB11890-89 |
|
54 |
Chlorobenzene |
Gas chromatography |
To be issued |
|
55 |
o-dichlorobenzene |
Gas chromatography |
To be issued |
|
56 |
p- dichlorobenzene |
Gas chromatography |
To be issued |
|
57 |
p-nitrochlorobenzene |
Gas chromatography |
GB13194-91 |
|
58 |
2,4-dinitro-1-chlorobenzene |
Gas chromatography |
GB13194-91 |
|
59 |
Phenol |
Gas chromatography |
To be issued |
|
60 |
m-cresol |
Gas chromatography |
To be issued |
|
61 |
2,4-dichlorophenol |
Gas chromatography |
To be issued |
|
62 |
2,4,6-trichlorophenol |
Gas chromatography |
To be issued |
|
63 |
di-butyl phthalate |
Gas, liquid chromatography |
To be issued |
|
64 |
di-octyl phthalate |
Gas, liquid chromatography |
To be issued |
|
65 |
Acrylonitrile |
Gas chromatography |
To be issued |
|
66 |
Total selenium |
2,3- diaminonaphthalene fluorimetric method |
GB-11902-89 |
|
67 |
Manure coliform index |
Multibarrel fermented method |
1) |
|
68 |
Total residual chlorine |
Spectrophotometry using N,N-diethyl-1,4 phenylenediamine
Titrimetric method using N,N- 1,4 phenylenediamine |
GB11898-89
GB11897-89 |
|
69 |
Total organic carbon (TOC) |
Non-chromatic dispersion infrared adsorption method Direct UV-fluorimetric method |
To be issued
To be issued |
|
Note: Before the national standards are issued, the following methods may be adopted temporarily.
1) “Standard Methods for the Examination of Water and Wastewater”, China Environmental Science Press, 1989.
2) “Technical Regulation of Environmental Monitoring”, NEPA.
3) The details see appendix D. |
6. The Implementation and Supervision of the Standard
6.1 The implementation of this standard is to be supervised by the administrative government authorities for environmental protection on the local county level or above.
6.2 When the implementation of national wastewater pollutant discharge standard can’t guarantee the function of water environment, the People’s government of province, autonomous region, municipality directly under the central government can issue regional water pollutant discharge standards which are more stringent than the national water pollutants discharge standard. The regional standard should be reported for the record to national administrative department for environmental protection.
Appendix A (Appendix of the Standard)
When the enterprise discharges two or more than two kinds of industry wastewater in the same discharge outlet, and the discharge standards of the same pollutant in various kinds of industry wastewater are different, the following method can be used to calculate the maximum allowable discharge concentration of the pollutant in the mixed wastewater (Cm).
Cm= (A1)
In which,
Cm—the maximum allowable discharge concentration of a certain pollutant in the mixed wastewater, mg/L;
Ci—the maximum allowable discharge concentration of a certain pollutant in wastewater of different industry, mg/L;
Qi—the maximum allowable discharge quantity in the different industry, m3/t (product)
(For the trades which are not included in the standard, the local environmental protection department and the corresponding department determine the maximum allowable discharge quantity through consultation.);
Yi—the output of a respective industry product (t/d, as monthly average).
Appendix B (Appendix of the Standard)
Calculation of the maximum allowable load of the pollutant in the industry wastewater:
Lminus=C×Q×10-3 (B1)
In which,
Lminus—the maximum allowable discharge load of the pollutant in the industry wastewater, kg/t (product)
C—the maximum allowable discharge concentration of a certain pollutant, mg/L;
Q—the maximum allowable discharge quantity of a certain industry, m3/t (product).
Appendix C (Appendix of the Standard)
Calculation of the total annual maximum allowable discharge quantity of a certain pollutant:
Ltotal=L1×Y× 10-3 (C1)
In which,
Ltotal—the maximum allowable annual discharge annual of a certain pollutant, t/a;
L1—the maximum allowable discharge load of a certain pollutant, kg/t (product);
Y—the checked annual output, t(product)/a.
Appendix D (Appendix of the Standard)
1. Determination of the Total Amount of Color Developer
---- 169 Color Formation Reagent Method
It is very difficult to detect the color developer in integrated wastewater discharged from film developing. The domestic and foreign methods introduced are usually applicable to the detection of developer in the developing water. This method can rapidly detect the color developer in integrated wastewater. If there are many kinds of color developers in wastewater, the result of this method is the total amount of the various color developers.
1. Principle
The color developer in the film developing wastewater can be oxidized by oxidant. When the oxide and water soluble color formation reagent are mixed in alkaline solution, they will rapidly couple to form dye. When the developers with different structure (TSS, CD-2, CD-3) couple with 169 color formation reagent to form dye, the maximum adsorption spectrum wavelength is 550nm, and it obeys the Bill law in the range of 0-10mg/L.
Take TSS for example, the reaction is as follows:
2. Instrument and Equipment
721 or similar type of spectrophotometer and 1cm colorimetric cell;
Measuring flask of 50ml, 100ml and 1000ml.
3. Reagent
(1) 0.5% color formation reagent: weigh 0.5g 169 color formation reagent and put it into the beaker with 100ml distilled water, add 1~2 grains of sodium hydroxide (NaOH) while agitating, then make them dissolve completely.
(2) Mixing oxidant solution: make CuSO4. 5H2O (0.5g), Na2XO3 (5.0g), NaNO2 (5.0g) and NH4Cl (5.0g) dissolve in 100ml distilled water successively.
(3) Standard solution: weigh 100mg photo color developer precisely (one of the most used in production), dissolve them in a little distilled water which has been dissolved 100mg Na2SO3 as protection reagent, then transfer into the measuring flask of 1000ml volume, add the distilled water to the graduation. The concentration of the standard solution is 0.1mg/ml. It must be prepared just before using.
4. Procedure
(1) Draw up the standard curve
Add different amount of the following developer standard solutions into six measuring flasks separately.
|
No |
The amount of standard solution (ml) |
The content equivalent to developer (mg/L) |
|
0 |
0 |
0 |
|
1 |
1 |
2 |
|
2 |
2 |
4 |
|
3 |
3 |
6 |
|
4 |
4 |
8 |
|
5 |
5 |
10 |
Add 1ml color formation reagent solution into the above mentioned six measuring flasks separately, add distilled water to the graduation, then add 1ml mixed oxidant solution separately, shake to uniformity. Determine the luminous densities of the dye produced from different samples at 550nm of spectrophotometer in five minutes (suppose the NO. “0” as zero), draw up the corresponding luminous density curve of the different developer content. The horizontal coordinates are 2, 4, 6, 8, 10 mg/L.
(2) Determination of water sample
Put two shares of water samples (normally 20ml) into two measuring flasks of 50ml separately. One is the water sample to be determined, the other is used as blank test. Add 1ml color formation reagent into former water sample to be determined, then add the distilled water to the graduations of the two flasks. The other procedures are the same as the drawing of the standard curve. Suppose the blank solution to be zero, determine the luminous density of water sample, check out the corresponding concentration on the standard curve.
5. Calculation
The concentration checked from the standard curve×50/a = the total amount of color developer in wastewater (mg/L) (D1)
In which,
a – the number of wastewater sample in ml.
6. Matters Needing Attention
(1) The luminous density of the created magenta dye is stable in eight minutes. So it’s appropriate to do the determination in five minutes after the dye created.
(2) The method excludes the black and white developer.
2. The Determination Method of the Total Amount of Developer and its Oxide
There exists different quantity of potash prussiate bleacher solution in film developing wastewater, which partly or completely oxidizes the discharged developer. So one situation is that there exist developer and its oxide in wastewater, the other situation is that there only exist lots of oxide but no developer. The result determined by the method is the total amount of developer and its oxide under the first situation, and is the content of oxide of original developer in wastewater under the second situation.
1. Principle
The developers most used normally have the structure as p-diphenol, p- aminophenol, p-diamino benzene compounds. They can be oxidized and hydrolysised to p-quinone. Bromine or chlorine bromine is used to oxidize the developer to the developer’s oxide. Then the iodometry is used to carry out the determination of iodine-starch colorimetry.
Take metol for example:
Quinone is a stronger oxidant. In acid solution, iodine ion quantitatively reduces p-benzene diquinone to p-benzene diphenol. The released equivalent iodine can be determined with colorimetry by use of starch that can change blue.
2. Instrument and Equipment
721 or similar type of spectrophotometer and 2cm colorimetric cell, the thermostate water bath bowl, the measuring flask of 50ml volume, the pipette with graduation of volume of 2ml, 5ml and 10ml.
3. Reagent
(1) Potassium bromate-potassium bromide with concentration 0.1N: weigh 2.8g potassium bromate and 4.0g potassium bromide, then use the distilled water to dilute to 1L.
(2) 1:1 phosphoric acid: add the same volume of distilled water into the phosphoric acid.
(3) Saturated sodium chloride solution: weigh 40g sodium chloride, then make them dissolve in 100ml distilled water.
(4) Potassium bromide with concentration of 20%: weigh 20g potassium bromide, then made them dissolve in 100ml distilled water.
(5) Phenol with concentration of 5%: dissolve 5ml phenol into 100ml distilled water.
(6) Potassium iodide solution with concentration of 5%: weigh 5g potassium iodide, then dissolve them into 100ml distilled water. (Prepare when using and then put them in dark.)
(7) Starch solution with concentration of 0.2%: weigh 1g soluble starch, add a little water and stir them evenly, pour the boiling water of 500ml, then boil them for 5 minutes. Add 0.2g salicylic acid in summer.
(8) Prepare Standard Solution
Weigh 0.276g p-diphenol precisely (molecular weight is 110.11g). If it is photo grade metol(molecular weight is 344.40g), weigh 0.861g, and photo grade TSS (molecular weight is 262.33g), weigh 0.656g. (Or calculate according to the molecular weight and purity of the reagent chemicals used), dissolve them in 25ml 6NHCl, then transfer them into measuring flask of 250ml. Add distilled water to the graduation. The concentration of the solution is 0.0100M.
4. Procedure
1). Draw up the standard curve
(1) Take 25ml of standard solution, add distilled water to dilute to 1000ml. The concentration of the solution is 0.00025M. That means there is 0.25μmol p-diphonel in every milliliter solution (solution A).
(2) Take 25ml of solution A, dilute it to 250ml with distilled water. The concentration of the standard solution is 0.000025M, that means there is 0.025μmol p-diphonel in every milliliter solution (solution B).
(3) Take six 50ml volume of measuring flasks, and add the standard diluted solution (solution B) 0, 0.1, 0.2, 0.3, 0.4, 0.5 μmol p-diphonel separately (that’s 4.0, 8.0, 12.0, 16.0, 20.0ml volume of solution B), add appropriate amount of distilled water, make the volume of solution in each measuring flask to be about 20ml.
(4) Add 2ml volume of 1:1 phosphoric acid by the pipette.
(5) Draw 5ml volume of saturated sodium chloride solution by the pipette.
(6) Draw 2ml volume of 0.1N potassium bromate-potassium bromide by the pipette; don’t touch the wall of the flask as much as possible. Wash the wall of the flask by a little of water, and shake evenly. The solution shall be pale yellow of bromide chloride, put it into water bathing bowl with the constant temperature at 35℃ for 15 minutes.
(7) Draw 2ml of potassium bromide solution with concentration of 20%, put into the measuring flask along the wall of the flask. After shaking evenly, place it into water bathing bowl of constant temperature at 35℃ for 5~10 minutes.
(8) Add 1ml volume of phenol solution with concentration of 5% rapidly by the dropper, shake evenly at once, make the color of bromine fade. (It is likely to generate white precipitate if adding slowly, it is unable to use colorimetric method).
(9) Lower the temperature: place it in the tap water to lower the temperature for three minutes.
(10) Add 2ml of newly prepared potassium iodide solution with concentration of 5% by the pipette, wash the wall of the flask. Place it into the dark cabinet for five minutes.
(11) Draw 10ml of starch indicator with concentration of 0.2%, add into the measuring flask, add distilled water to graduation. After covering the lid and shaking it evenly, place it into the dark cabinet for 20 minutes.
(12) Place the chromophoric test solution into the colorimetric cell with volume of 2ml separately. At the wavelength of 570nm of the spectrophotometer, take the reagent blank as zero, then determine the luminous densities of the five solutions separately, and draw up the standard curves. The horizontal coordinates are 0.1, 0.2, 0.3, 0.4, 0.5μmol/50ml.
2) Determination of the water sample
Take appropriate amount of water sample (about 1~10ml) into 50ml volume of the measuring flask, and add the distilled water to about 20ml. Add 20ml volume of distilled water into another 50ml the measuring flask as the reagent blank. The following procedures are carried out according to procedure (4)~(12), determine the luminous densities of the water samples, check out the number of the microgram molecular in 50ml water sample from the curve
3) Determination of water sample needed eliminating the interference
When the water samples contain chromium (VI) that affects the determination, chromium (VI) can be reduced to chromium (III) by the sodium nitrite. Then eliminate the interference of superfluous sodium nitrite to this experiment by use of excess urea. Thus the interference of chromium (VI) can be eliminated.
Take appropriate amount of water sample (about 1~10ml) precisely, put it into 50ml volume of the measuring flask, add the distilled water to about 20ml, add 2ml 1:1 phosphoric acid, then add three drops of 10% sodium nitrite, shake fully, put it into the water bathing bowl with constant temperature of 35℃ for 15 minutes. Then add 2ml 20% urea, shake fully, put it into the water bathing bowl with constant temperature of 35℃ for 10 minutes. The following operation shall be carried out according to procedures (5)~(12), determine the luminous density, check out the number of the microgram molecular contained in 50ml water sample from the curve.
5. Calculation
Calculate the total amount of the developer and its oxide in water sample (refer as p-diphenol) by the following formula:
C(mg/L)= (D2)
6. Note
(1) The experiment requires careful and serious operation because of its many procedures and long time needed.
(2) The glass instruments used must be cleaned by detergent.
(3) The temperature of water bathing shall be kept at 35℃±1℃ exactly, the reaction time of every procedure should be controlled accurately.
(4) After potassium bromate-potassium bromide is added, the distilled water must be used to wash the wall of the measuring flask. Otherwise, the residual potassium bromate will react with potassium iodide to produce iodine, which will increase the luminous density.
(5) In wastewater without containing the chromium ion, the water sample need not be treated and can be determined directly.
(6) If the concentration of water sample is too high, it should be determined after the dilution is done in advance.
3.Determination of Element Phosphor--Molybdenum-Blue Colorimetric Method
1. Principle
The element phosphor is oxidized to molybdenum phosphate after extracted. The molybdenum phosphate is reduced to blue complex compound by fin bichloride. Its sensitivity is higher than vanadium molybdenum phosphate colorimetric method, and it is easy to concentrate. After concentration, it can improve the detect reliability of element phosphor whose concentration is lower than 0.1mg/L, and it can reduce the interference.
When the contents of arsenide, silicide and sulfide in water sample is 100, 200 and 300 times of the phosphor content separately, there is no clear interference to the method.
2. Instrument and reagent:
Instrument:
spectrophotometer, 3cm colorimetric cell
Colorimetric tube: 50ml
Separating funnel: 60, 125 and 250ml
Ground flask: 250ml
Reagent:
the following reagents are the analytic reagents:
benzene, perchloric acid, potassium bromate, potassium bromide, glycerine, fin bichloride, ammonium molybdate, potassium dihydrogen phosphate, acetate butyric ester, sulphuric acid, nitric acid, absolute alcohol, phenolphthalein indicator.
3. Prepare the solution:
(1) Potassium dihydrogen phosphate standard solution: weigh 0.439g dried potassium dihydrogen phosphate precisely, dissolve them in a little amount of water, transfer into 1000ml volume of the measuring flask, fix the volume. The concentration of PO4-3 –P of the solution is 0.1mg/ml. Take 10ml of the solution to 1000ml measuring flask, fix the volume, then you will get the potassium dihydrogen phosphate standard solution with the concentration of PO4-3 –P of 1μg/ml.
(2) Potassium bormate-potassium bromide solution: dissolve 10g-potassium bromate and 8g potassium bromide into 400ml water.
(3) 2.5% ammonium molybdate solution: weigh 2.5g ammonium molybdate, add 70ml 1:1 sulfuric acid solution, add 30ml water after ammonium molybdate is dissolved.
(4) 2.5% tin bichloride glycerine solution: dissolve 2.5 tin bichloride into 100ml glycerine (can be heated in water bathing to improve its dissolving).
(5) 5% ammonium molybdate solution: dissolve 12.5g ammonium molybdate into 150ml water, pour the solution into 100ml 1:5 nitric acid solution slowly after it has been dissolved.
(6) 1% tin bichloride solution: dissolve 1g tin bichloride solution into 15ml hydrochloric acid, add 85ml water and 1.5g ascorbic acid (can be kept for 4~5 days).
(7) 1: 1 sulfuric acid solution, 1:5 nitric acid solution, 20% sodium hydroxide solution.
4. Determination procedures:
(1) When the concentration of element phosphor in wastewater is higher than 0.05mg/L, the water phase can be used for colormetric analysis directly by the following procedures:
1) Pretreatment of water samples
a) Extraction: Take 10~100ml water sample into 125ml or 250ml volume of the separating funnel containing 25ml benzene. After shaking it for five minutes, place it motionlessly until the phases appear. Take the water phase into another separating funnel containing 15ml benzene, place it motionlessly after shaking it for two minutes. Abandon the water phase, mix the benzene phase into the first separating funnel. Add 15ml water, place it motionlessly after shaking it for one minute. Abandon the water phase, wash the benzene phase for six times.
b) Oxidation: Add 10~15ml potassium bromate-potassium bormide solution and 2ml 1:1 sulfuric acid into the benzene phase, shaking for five minutes, add 2ml perchloric acid after place them motionlessly for two minutes, shake for five minutes, transfer into a 250ml of the ground flask. Heat slowly on the electric hot board to drive the excessive perchloric acid and bromine (don’t make the sample spattered or dried), take the flask from board and make cool when the white vapor diminishes. Add a little amount of water and a drop of phenolphthalein indicator, neutralize them to pink color by the 20% sodium hydroxide solution. Add a drop of 1:1 sulfuric acid solution until the pink color vanishes, transfer them into the measuring flask, dilute them to graduation with distilled water (determine the dilution volume according to the content of element phosphor).
2) Colorimetry:
Transfer appropriate amount of above diluted solution into 50ml colorimetric tube, add 2ml 2.5% ammonium molybdate and six drops of 2.5% tin bichloride-glycerine solution, add water to dilute them to the graduation, mix them evenly, place them at 20~30℃ for 20 to 30 minutes, pour them into 3cm colorimeter cell, and take the blank reagent as zero, determine the luminous density at 690nm of spectrophotometer.
3) Draw the curve of direct colorimetric method:
(a) Transfer appropriate amount of potassium dihydrogen phosphate standard solution into 50ml colorimetric tube, make the amount of PO4-3 –P to be 0, 1, 3, 5, 7,……. 17μg separately, determine the light density.
(b) Take the content of PO4-3 –P as the horizontal ordinate, the luminous density as the vertical ordinate, draw the curve of direct colorimetric method.
(2) Adopt the organic phase extraction colorimetric method when the concentration of element phosphor in wastewater is lower than 0.05mg/L. Operate according to the following procedures:
1) Pre-treatment of water sample:
Extraction and colorimetry: transfer the appropriate amount of diluted oxidized solution into 60ml separating funnel containing 3ml 1:5 nitric acid solution. Add 7ml 15% ammonium molybdate solution and 10ml acetate butyric ester, shake for one minute, and abandon the water phase. Add 2ml 1% tin bichloride solution into the organic phase, shake them evenly. Then add 1ml anhydrous alcohol, move the separating funnel softly, make the water drops down, draw off water phase, pour organic phase into 3cm colorimetric cell, at the 630 or 720nm wave length of spectrophotometer, take the reagent blank as zero and determine the luminous density.
2) Drawing of organic phase extraction colorimetric curve.
(a) Transfer the appropriate amount of potassium di-hydrogen phosphate standard solution into 60ml separating funnel, make the content of PO4-3 –P to be 1, 2, 3, 4, 5μg separately, add a little amount of water, the following procedures are the same as above mentioned extraction colorimetric method.
(b) Take the content of PO4-3 –P as horizontal ordinate, the density as vertical ordinate; draw the curve of direct colorimetric method.
5. Calculation:
Calculate the number of milligram of element phosphor in 1L wastewater with the direct colorimetric method and the organic extraction colorimetric method by the following formula:
P= (D3)
In which,
G—the amount of element phosphor checked from the curve, μg;
V1—the volume of the gathered wastewater sample, ml;
V2---the diluted volume after oxidization of waste wastewater sample, ml;
V3--- the volume of diluted solution taken for colorimeter, ml.
6. Precision:
The difference of the two results determined in parallel should not exceed 10% of the smaller one.
Take the arithmetic mean of the two results determined in parallel as the content of element phosphor in water sample. The determined result takes two significant digits.
7. Preservation of sample:
Adjust pH of water sample to 6~7 after sampling. It can be kept for 48 hours in plastic or glass bottle. |
