INCREASES IN EFFICIENCY OF BIOLOGICAL PURIFICATION OF THE CUTTING FLUID-CONTAINING SEWAGE BY USE OF SELECTIVE
DESTRUCTORS OF SURFACTANTS
Ilnar Abuzarovich Nasyrov1, Nina Nikolaevna Smirnova1, Alena Alexandrovna Inyusheva2, Albina Rashitovna Sadykova1
1Kazan Federal University, Naberezhnye Chelny Institute,
2 LLC «PEK region 2»
e-mail: chem_aleb@mail.ru ABSTRACT
In this paper is considered influence of the surfactants entering a compounding of cutting fluid on the representative of biocenoses of active silt of treatment facilities and open reservoirs Daphnia magna Straus. Work was carried out on artificial selection of 33 destructors of coolant for the purpose of obtaining strains with directional action on biodegradation of surfactants in the utilization of coolant- containing wastewater. The activity of selective destructors on modular samples consisting of industrial oil and surfactants in concentrations typical for emulsion coolant formulations was studied. Acute toxicity of 3 brands of surfactants (nonoxynols, sodium lauryl sulfate, ammonium lauryl sulfate) was found in the dilutions 1:10, 1: 50,1: 100,1: 1000. For receiving selective destructors surfactant community of the microorganisms which are previously allocated from workers cutting fluid was subjected to influence of bactericides by Vazin, Novamet in the concentration exceeding norm by 10 times. Representatives of the survived population adapted to surfactants solutions as to the only power supply. As a result of the carried-out work 5 strains of microorganisms which activity investigated surfactant on dynamics of mass concentration have been received. Decrease in concentration of all 3 surfactants brands under the influence of the received strains is revealed, but most intensively microorganisms decomposed nonoxynols that it is possible to explain with long-term adaptation of redutsent to this substance.
Keywords: cutting fluid, sodium laurylsulphate, ammonium laurylsulphate, nonoxynols, surfactant, toxicity, microorganisms.
INTRODUCTION
At production and processing of metal details lubricant cooling liquids are applied to lubricant and protection against corrosion. They represent the multicomponent systems containing a basic basis (water, mineral oil) and the additives providing a complex of physical and chemical, technological and operational properties [1].
The fulfilled cutting fluid solutions are the oil emulsions containing the dissolved and emulsified oil products and mineral oils, emulsifiers, surfactant, etc. They are divided by concentration of the main pollution (oil) on low-concentrated and concentrated. The low-concentrated drains are formed when washing metal products after their heat treatment. The concentrated sewage contains up to 50 g/l of oils.
These are waste cutting fluid and also the waste washing solutions representing resistant emulsions like
"oil in water". Their education makes 0,5 — 200 m3/days depending on enterprise capacity and type of his production.
The problem of utilization of the cutting fluid -containing sewage constituting ecological danger not only to a biocenosis of reservoirs, but also active silt of treatment facilities is relevant. Volumes of the cutting fluid-containing sewage directly depend on bioproofness of emulsions.
Biological sewage treatment is one of the most universal and ecologically expedient ways of prevention of hit to the environment cutting fluid by their transfer to biological molecules and the most plain inorganic substances, returning, thus, xenobiotics in natural cycles [2].
One of ways of an intensification of process of biodegradation of components of sewage is use of the biologically active agents (BAA) as a stimulator of process of biodegradation of pollution.
Application of BAA increases efficiency and quality of sewage treatment, reduces terms of start of objects of biological cleaning, for example aerotenok and biofilters, in operation, expands possibilities of use of biological cleaning in the conditions of low temperatures and protects the cultures of active silt and a biological film from influence.
However, all surfactants complicate process of purification of waste water and reduce his quality. It is connected with the fact that the majority of surfactants can't be spread out in the biological way therefore under their action the overall performance of constructions of biological cleaning decreases as they lower activity of bacteria and microorganisms of active silt and oxidation processes are slowed down.
The most known anionic surfactant are laurylsulphates (most often – sodium laurylsulphate, sometimes – ammonium). This connection with rather aggressive chemical properties capable to cause an allergy, and at hit in an organism of large numbers his damage of lungs. Chemical formula C12H25SO4Na [3].
METHODS
Determination of toxicity of surfactants solutions was carried out according to requirements of a method [4]. Allocation of pure cultures of microorganisms was carried out by Koch's method. For determination of ability of strains to subject degradations surfactant used a colorimetric method [5]. By means of this method measured mass concentration surfactant within 21 days.
In order to perform the chemical mutagenesis, parallel samples of the freshly prepared Inkam-1 coolant up to 106 cells / ml with the addition of bactericides Vazin (3%) and Novamet (1%) were inoculated with a 24-day mixture of microorganisms previously extracted from emulsion fluids from the Engine Plant.
Control of the population size was carried out by sowing meat-peptone agar medium with the subsequent calculation of the total number of microorganisms (TOM, cell / ml). Microorganisms of again growing population were adapted to surfactants solutions as the only power supplies.
For identification of activity of selective destructors modular solutions from industrially oil and surfactant in the concentration characteristic of compoundings cutting fluid in which brought destructors also to TOM = 106 cell/ml have been prepared.
At the received selective destructors studied morphological, cultural, biochemical properties according to the standard microbiological methods
RESULTS AND DISCUSSION
The first stage of work was studying of toxicity surfactant, being a part of a compounding emulsion cutting fluid, on test organisms which are representatives as active silt and a biocenosis of water ecosystems [6]. Control was the cultivation water with the test object. For the study P2 climatostat was used.
The received results are presented in tables 1-3.
dilution рН Daphnia mortality, %
toxicity 0,5 hour 1 hour 2 hour 3 hour 4 hour 5 hour 24 hour 48 hour
1:10 5,28 80 100 - - - acute
1:20 5,30 60 80 100 - - - acute
1:50 5,35 20 70 100 - - - acute
1:100 5,36 10 50 100 - - - acute
1:1000 5,30 0 0 0 0 0 0 0 0 absent
control 8,01 0 0 0 0 0 0 0 0 absent
Table 2. Toxicity of ammonium lauryl sulfate
dilution рН Daphnia mortality, %
toxicity 0,5 hour 1 hour 2 hour 3 hour 4 hour 5 hour 24 hour 48 hour
1:10 5,41 100 - - - acute
1:20 5,46 100 - - - acute
1:50 5,50 90 100 - - - acute
1:100 5,52 100 - - - acute
1:1000 5,56 0 0 0 0 0 0 0 0 absent
control 8,01 0 0 0 0 0 0 0 0 absent
Table 3. Toxicity of nonoxynols
dilution рН Daphnia mortality, %
toxicity 0,5 hour 1 hour 2 hour 3 hour 4 hour 5 hour 24 hour 48 hour
1:50 5,19 20 90 100 - - - acute
1:100 5,25 10 70 90 100 - - - - acute
1:1000 5,30 0 10 50 90 100 - - - acute
control 8,01 0 0 0 0 0 0 0 0 absent
The results of researches presented in tab. 1-3 demonstrate acute toxicity all three investigated surfactant in dilutions from 1:10 to 1:1000. However, in test with nonoxynols (a component of compoundings of many cutting fluid brands) 100% death the test objects was observed during shorter time (from 2 to 4 hours), than in tests with laurylsulphate of sodium and laurylsulphate of ammonium.
In structure cutting fluid surfactants are used as emulsifiers of industrial oils. Recently for decrease in smoke in shops industrial oil in a compounding of concentrates of emulsions is changed for vegetable oil.
Results of toxicity of compositions surfactant - oil are presented in tab. 4-7.
Table 4. Toxicity of composition nonoxynols - industrial oil IM-40
dilution рН
Daphnia mortality, %
toxicity 0,5
hour 1 hour
2 hour
3 hour
4 hour
5 hour
24 hour
48 hour
168 hour
without 7,02 100 - - - acute
1:100 5,81 0 100 - - - acute
1:1000 5,56 0 50 100 - - - acute
1:10000 5,62 0 0 10 40 40 40 50 90 100 acute
control 6,63 0 0 0 0 0 0 0 0 0 absent
Apparently from data of table 4, acute toxicity nonoxynols with industrial oil IM-40 was observed in test without dilution and in dilution 1:100, 1:1000 as 100% death of a test object came within 2 hours from the beginning of an experiment and 48 hours later in cultivation 1:10000 has made 90% of death.
Table 5. Toxicity of composition nonoxynols - vegetable oil
dilution рН
Daphnia mortality, %
toxicity 0,5
hour 1 hour
2 hour
3 hour
4 hour
5 hour
24 hour
48 hour
168 hour
without 7,06 100 - - - acute
1:100 5,63 0 100 - - - acute
1:1000 5,56 0 30 80 90 100 - - - - acute
1:10000 5,80 0 0 0 0 0 0 0 0 70
issue (+11%)
acute
control 6,63 0 0 0 0 0 0 0 0 0 absent
The comparative analysis of these tab. 4-5 shows decrease in toxicity when replacing industrially of oil on vegetable. Confirmation to it is the test object issue in cultivation 1:10000.
Table 6. Toxicity of composition sodium lauryl sulfate - industrial oil IM-40
dilution рН
Daphnia mortality, %
toxicity 0,5
hour 1 hour
2 hour
3 hour
4 hour
5 hour
24 hour
48 hour
168 hour
without 6,92 30 100 - - - acute
1:100 5,70 0 0 0 10 20 30 50 70 90 acute
1:1000 5,51 0 0 0 10 10 10 20 40 50 chronic
1:10000 5,55 0 0 0 0 0 0 0 0 60 chronic
control 6,63 0 0 0 0 0 0 0 0 0 absent
Apparently from data of table 6, the acute toxicity of laurylsulphate of sodium with IM-40 was observed in test without dilution and in dilution with concentration 1:100 as 70% death of a test object came within 48 hours from the beginning of an experiment. The chronic toxicity was observed in dilution 1:1000 and 1:10000.
Results of tab. 1-6 allow to explain the reason of incomplete clarification of the surfactant-containing sewage and especially drains of machine-building enterprises.
For allocation of selective destructors of the cutting fluid -containing sewage containing surfactant 33 strains of the microorganisms allocated from workers cutting fluid which were applied at the plants have been used [7].
Population of these microorganisms was exposed to a chemical mutagenesis bactericides Vazin and Neomet who entered into tests on a maximum of an exponential phase of development of microbic population [8,9]. Experiment time - 105 days. The obtained data on dynamics of number of microorganisms are submitted in fig. 1.
Figure 1 – Dynamics of number of a microbiocenosis cutting fluid at influence of bactericidal additives (TOM - total of microorganism).
For further researches 4 phases of development which adapted to surfactant as to the power supply used microorganisms. Total of microorganisms in tests surfactant are presented in tab. 7.
Table 7. The number of destructors in surfactants solutions.
name of test TOM, cell/ml in dilution at crops
without dilution 10-1 10-2 10-3
sodium lauryl sulphate growth 21 х 101 82,625 х 102 290 х 103 nonoxynols growth 5390 х 101 2412,5 х 102 500 х 103 ammonium laurylsulphate growth 1000 х 101 190 х 102 135 х 103 ammonium laurylsulphate growth 2816,3 х 101 2266 х 102 28400 х 103
As a result of the conducted researches 7 strains of destructors with good growth and on meat-peptonnom an agar (tab. 7) have been received. The name of strains and their property (morphological, cultural, biochemical) will be described in the patent.
The activity of selective destructors determined by change of mass concentration surfactant is presented in tab. 8.
Time
With selective destructors, mg / dm Without selective destructors, mg / dm
nonoxynols + IM40
ammonium lauryl sulfate
+ IM40
sodium lauryl sulfate
+ IM40
nonoxynols + IM40
ammoniu m lauryl sulfate + IM40
sodium lauryl sulfate
+ IM40
After 7 day 1868 21154 16506 2242,6 22932,1 5320,4
After 14 day 293,3 13162 8017,4 2242,6 22932,1 5320,4
After 21 day 38,9 4052,7 1142,3 2242,6 22932,1 5320,4
Results of laboratory researches demonstrate activity of selective destructors in the course of biodegradation surfactant. Most intensively microorganisms decompose nonoxynols that it is possible to explain with long-term adaptation of redutsent to this substance.
SUMMARY
When studying toxicity surfactant, being a part of a compounding emulsion cutting fluid it is revealed that sodium laurylsulphate, laurylsulphate of ammonium and nonoxynols have acute toxicity in dilutions 1:10, 1:20, 1:50 and 1:100, mortality occurred within 4 hours. Have carried out selection of microflora cutting fluid for the purpose of allocation of the microorganisms destroying surfactant and have received 5 strains of destructors. Results in on dynamics of mass concentration surfactant have shown reduction concentration surfactant with the maintenance of microorganisms in nonoxynols cultivations since 1868 to 38,9 mg/dm3, sodium laurylsulphate from 21154 to 4052 mg/dm3 and laurylsulphate of ammonium from 16506 to 1142 mg/dm3, in control samples decrease surfactant wasn't observed.
CONCLUSIONS
Addition of the destructors received as a result of selection to community of active silt of treatment facilities will promote an intensification of biological sewage treatment of machine-building enterprises, surfactant will reduce contents, will improve quality of a surface water and also will keep a biocenosis of a reservoir and health of the population.
ACKNOWLEDGEMENTS
The work is performed according to the Russian Government Program of Competitive Growth of Kazan Federal University.
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