WO2013008163A1 - Process for quantitatively determination of total chlorine in a matrix - Google Patents
Process for quantitatively determination of total chlorine in a matrix Download PDFInfo
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- WO2013008163A1 WO2013008163A1 PCT/IB2012/053474 IB2012053474W WO2013008163A1 WO 2013008163 A1 WO2013008163 A1 WO 2013008163A1 IB 2012053474 W IB2012053474 W IB 2012053474W WO 2013008163 A1 WO2013008163 A1 WO 2013008163A1
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- process according
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000460 chlorine Substances 0.000 title claims abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 26
- 239000011159 matrix material Substances 0.000 title claims abstract description 22
- 241000575946 Ione Species 0.000 claims abstract description 17
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 6
- AEBYJSOWHQYRPK-UHFFFAOYSA-N 1,1'-biphenyl;sodium Chemical group [Na].C1=CC=CC=C1C1=CC=CC=C1 AEBYJSOWHQYRPK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 4
- 230000002596 correlated effect Effects 0.000 claims abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims abstract 4
- 238000004320 controlled atmosphere Methods 0.000 claims abstract 3
- 150000002334 glycols Chemical class 0.000 claims abstract 3
- 238000001556 precipitation Methods 0.000 claims abstract 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 claims description 46
- 239000003921 oil Substances 0.000 claims description 30
- 235000019198 oils Nutrition 0.000 claims description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002689 soil Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- -1 asphalts Substances 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000010720 hydraulic oil Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 241001465754 Metazoa Species 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 230000000035 biogenic effect Effects 0.000 claims 1
- 239000005388 borosilicate glass Substances 0.000 claims 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims 1
- 239000000446 fuel Substances 0.000 claims 1
- 239000000314 lubricant Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000725 suspension Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- BTAGRXWGMYTPBY-UHFFFAOYSA-N 1,2,3-trichloro-4-(2,3,4-trichlorophenyl)benzene Chemical compound ClC1=C(Cl)C(Cl)=CC=C1C1=CC=C(Cl)C(Cl)=C1Cl BTAGRXWGMYTPBY-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000011002 quantification Methods 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229920003237 carborane-containing polymer Polymers 0.000 description 6
- 235000010333 potassium nitrate Nutrition 0.000 description 6
- 239000004323 potassium nitrate Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000011088 calibration curve Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 108010094028 Prothrombin Proteins 0.000 description 2
- 108010000499 Thromboplastin Proteins 0.000 description 2
- 102000002262 Thromboplastin Human genes 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000003018 immunoassay Methods 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 2
- ZOJJJVRLKLQJNV-UHFFFAOYSA-N 2-(2,2-dimethoxyethoxy)-1,1-dimethoxyethane Chemical compound COC(OC)COCC(OC)OC ZOJJJVRLKLQJNV-UHFFFAOYSA-N 0.000 description 1
- 108010014172 Factor V Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001987 mercury nitrate Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/24—Earth materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Specific substances contained in the oils or fuels
Definitions
- This invention relates to a process for the quantitative determination of the total chlorine in a matrix, possibly expressed as polychlorinated biphenyls (PCBs) equivalent, in particular in insulating liquids, oils in general, soils or metal components of apparatuses, foods, products for agriculture, in compliance with Best Available Techniques (BAT) and Best Environmental Practices (BEP) guidelines for Smart Field Test (SFT).
- PCBs polychlorinated biphenyls
- the PCBs can be absent ( ⁇ 2 mg kg "1 ) in fresh insulating liquids and in oils in general, whereas - for what oils in operation used in equipment are concerned - the concentration must be below the limits prescribed by laws and local regulations (ex. ⁇ 50 mg kg "1 according to Directive 96/59/EC, etc.).
- PCBs in a matrix require a complex, expensive and extended process, starting with a representative sampling with a throw away kit, the shipment of the sample to an accredited laboratory operating according to specific methodologies (ex. IEC 61619, EN 12766) equipped with expensive apparatuses (ex. Gas chromatographs with ECD sensors) and specialised operators.
- -kit Dexsil® (USA) designated as Clor-N-soil, i. e, field tests for the screening of PCBs in soil;
- the kit Clor-N-Oil is a colorimetric method having the main limitation of being unable to quantify the concentration of total chlorine in the oil, but only the compliance with a prefixed threshold value (ex. 500, 50 o 20 mg kg "1 ).
- the kit Clor-N-Oil, L 2000 uses highly toxic substances such as, for example, nickel nitrate and mercury nitrate.
- the kit Clor-N-Oil requires a substantial amount of oil (at least 10 ml) thus determining a corresponding amount of waste to be disposed of.
- the Dexsil® L2000 is able to provide a quantification of the total chlorine with the cost of the use of a much more expensive dedicated instrument (with respect to the Clor-N-Oil) equipped with a selective electrode for chloride iones, capable of solving the limitations linked to the kit Clor-N-Oil.
- the kit for immunoassay by Hach based upon enzymatic reactions, is of a purely semiquantitative nature and it can be applied to solids only and not to oils.
- the sample containing the halogen to be analysed is weighted in a glass bulb and is placed in a separating "funnel" - i.e.
- XP55015103 describes the Volhard method for the determination of chlorine, expressly specifying that the colloidal particles that are formed when the silver iones are added to solutions of chloride are too small to be removed by filtration.
- the object of this invention is to provide a process capable of overcoming the criticalities described above.
- the process of the invention presents the advantages or requiring lesser investments, as well as using not much toxic substances and a reduced amount of sample, for the quantitative determination, in particular by colorimetric and/or electro-chemical way, of the total content of chlorine - i.e. PCBs screening - in an organic liquid matrix, which could be possibly derived from a solid matrix to be analysed (soils or surfaces - wipe test).
- total chlorine is intended as the concentration of organic and inorganic chlorine present in the matrix sampled and measured as total chlorides.
- PCB equivalent is intended the concentration of PCBs as equivalent mixture of PCBs expressed as typical Aroclor 1260 obtained by the conversion of the total chlorides through known conversion coefficients, capable of ensuring zero "false negatives” and to accept the "false positives” caused by the possible presence of other chlorinated compounds not classifiable as PCBs.
- PCB Screening is intended the evaluation of the total chlorine correlated to the potential mixtures of PCBs, present in the matrixes, with a result exceeding the prescribed limits, such to require a subsequent and specific quantitative determination of the PCBs, according to the above mentioned methodologies (IEC 61619, EN 12766 etc.).
- representative sampling of liquids or solids is intended the sampling of one or more determined amounts of liquid or solid matrix (oil or soil, for example, and in compliance with the laws and technical norms of the sector) in such a manner that the value of the concentration of PCBs determined is applicable to the entire matrix as a whole.
- peel test sampling is intended the transfer, through controlled rubbing, of the PCBs from surfaces on which it has been deposited onto appropriate throw away tissues soaked with solvents (hexane, acetone or mixtures) from which it is easily extractable and quantifiable as mg of PCBs for a normalised surface (ex. 100 cm ).
- micro dispenser is intended a mechanical/electronic apparatus for the precise dosing of discrete and variable aliquots of titration solution.
- the matrices on which the process of the invention can be done are, for example, insulating oils with mineral or synthetic base, lubricating oils, hydraulic oils, vegetable oils, natural or synthetic esters and solutions obtained from metal parts, soil and solid surfaces in general.
- the quantitative determination of the total concentration of chlorine and the PCBs screening occurs preferably by colorimetric and/or potentiometric way.
- the process of the invention is based essentially upon a series of simple operational phase of conversion of the organic chlorine into inorganic chlorine through the reaction between 5 ml of oil (50% less with respect to the 10 ml of Clor-N-Oil, critical factor III) and a pre- dosed micro dispersion of sodium biphenyl or sodium naphthalene in a glycol or a derivative of it (normally dimethoxy ethyl ether also designated as diglyme), kept in an inert atmosphere in a sealed gastight disposable vial, in order to ensure for a long time the surprising performances in terms of limits of quantification, repeatability and reproducibility of the invention.
- the possibility of keeping the sodium biphenyl or naphthalene in inert atmosphere in a sealed disposable vial proved the simplification of the analytical methodology with respect to the kit Dexsil® (criticality V) since it reduces the number of parts and analytical operations.
- the chlorides obtained are extracted by a watery solution containing non-toxic potassium nitrate (and not mercury or nickel nitrate, cf. Critical factor II) and sulphuric or nitric acid, added to the vial after opening it. Then, the extraction solution is filtered through a 0.45 ⁇ nylon or teflon filter into a first container containing a pre-dosed volume of watery solution with a known concentration of silver nitrate.
- the products of the reaction are filtered through an additional 0.45 ⁇ teflon or nylon filter, into a second container for the quantification of the chlorine by a colorimetric way through titration with a 0.1 M solution of potassium thiocyanate added by a micro doser, with the presence of ferric sulphate.
- the latter can be done by electrochemical way, by a selective electrode for silver iones. In case of a colorimetric quantitative determination, at the moment the equivalent point is reached, the solution under examination turns from colourless into orange.
- the chlorides of such solution are caused to precipitate with an excess of silver nitrate and the residual silver iones are quantified by one of the above mentioned methods.
- the relevant chlorinated compounds must be pre-emptively extracted by washing with a known amount of a solvent, such as for example, hexane, heptane, trimethyl pentane, acetone, ethyle ether. So, a liquid matrix is obtained, which is subject to the same process describe above.
- the so called wipe test i.e. a mechanical-chemical removal of chlorinated organic compounds by using a disposable tissue soaked with hydrocarbon solvent (ex. hexane, acetone and mixtures) is used. These components are then extracted from the tissue by the addition of an hydrocarbon solvent, as for example, heptane or trimethyl pentane, obtaining a liquid matrix, which is subject to the same process described above.
- hydrocarbon solvent as for example, heptane or trimethyl pentane
- the sodium biphenyl or naphthalene complex is specifically prepared in an appropriate sealed vial in which an oxygen and carbon dioxide-free atmosphere is ensured.
- the total chlorine can be determined with high levels of repeatability a reproducibility both in the field and in laboratory, involving non- specialised personnel and without using expensive and bulky dedicated equipment, such as gas chromatographs with ECD probes (as required by complex authorisations for the presence radioactive isotope Ni 63). Thanks to this, it is possible, in particular, to measure values of total chlorine and PCBs screening between 2 through 1000 mg kg "1 (and beyond with an appropriate dilution) in the oils.
- the process of the invention proved to be surprisingly as the simplest, economical and fast response under all the application scenarios, solving the critical factors described above, for the determination of total chlorine and PCBs screening in compliance with the guidelines of Best Available Techniques (BAT) and Best Environmental Practices (BEP) for Smart Field Test (SFT).
- BAT Best Available Techniques
- BEP Best Environmental Practices
- SFT Smart Field Test
- figure 1 is a graph showing the comparison between the results obtained on exhausted mineral insulating oils applying the colorimetric technique of this invention and the gas chromatography ECD in accordance with norm IEC 61619 and EN 12766 (with error bars),
- figure 2 is an example of the calibration curve usable in the method for the colorimetric determination of the invention with the concentration of the PCBs indicated as a function of the micro litres of titration solution added (potassium thiocyanate 0.05 or 0.1 M) in the typical case of an exhausted mineral oil, and
- figure 3 is an example of calibration curve usable with the potentiometric determination method of the invention with concentration of PCBs Aroclor 1260 indicated as a function of the concentration of the residual silver iones, in the case of a typical exhausted mineral oil.
- the separation into two phases is awaited for about 10 minutes, than transfers the whole into a 20 ml disposable syringe without the piston, to the end of which a 0.45 ⁇ filter is placed.
- the watery phase is in this manner separated from the oily phase and directly transferred in a first disposable dark glass container containing a prearranged amount of solution of AgN0 3 0,1 M (500 ⁇ ).
- the suspension turns considerably cloudy; the first container is lightly shaken for a few seconds and the content is transferred into a 10 ml syringe without the piston to the low end of which a 0.45 ⁇ filter is placed.
- the suspension is filtered and transferred into a second 20 ml container filled with a 100 ⁇ solution of indicator Fe 2 (S0 4 )3; the solution turns pale-yellow.
- a solution of KSCN 0.1 M is added with doses of 10 ⁇ at a time; gradually, a white precipitated is formed. After adding 220 ⁇ , the suspension turns orange.
- the coefficient of conversion obtained from the calibration line of the method (cf. Fig.2) it was calculated that such value corresponds to a concentration of 252 mg kg "1 of PCBs equivalent Aroclor 1260.
- the separation into two phases is awaited for about 10 minutes, than transfers the whole into a 20 ml disposable syringe without the piston, to the end of which a 0.45 ⁇ filter is placed.
- the watery phase is in this manner separated from the oily phase and directly transferred into a first disposable dark glass container containing a prearranged amount of solution of AgNC"3 0,1 M (500 ⁇ ).
- the suspension turns imperceptibly cloudy; the first container is lightly shaken for a few seconds and the content is transferred into a 10 ml syringe without the piston to the low end of which a 0.45 ⁇ filter is placed.
- the suspension is filtered and transferred into a second 20 ml container filled with a 100 ⁇ solution of indicator Fe 2 (S0 4 )3; the solution turns a very pale-yellow.
- a solution of KSCN 0.1 M is added with doses of 10 ⁇ at a time; gradually, a white precipitated is formed. After adding 420 ⁇ , the suspension turns orange.
- the coefficient of conversion obtained from the calibration line of the method (cf. Fig.2) it was calculated that such value corresponds to a concentration of 34 mg kg "1 of PCBs equivalent Aroclor 1260.
- the separation into two phases is awaited for about 10 minutes, than transfers the whole into a 20 ml disposable syringe without the piston, to the end of which a 0.45 ⁇ filter is placed.
- the watery phase is in this manner separated from the oily phase and directly transferred into a first disposable dark glass container containing a prearranged amount of solution of AgN0 3 0,1 M (500 ⁇ ).
- the suspension turns considerably cloudy; the first container is lightly shaken for a few seconds.
- the residual concentration of silver iones is determined using a selective electrode of silver iones.
- the concentration of chloride iones is determined by the coefficient of conversion obtained from the calibration curves of the method (cf. Fig.3). In this case a value of 284 kg "1 of PCBs equivalent Aroclor 1260 was obtained.
- the watery phase is in this manner separated from the oily phase and directly transferred into a first disposable dark glass container containing a prearranged amount of solution of AgN0 3 0,1 M (500 ⁇ ).
- the suspension turns considerably cloudy; the first container is lightly shaken for a few seconds.
- the residual concentration of silver iones is determined using a selective electrode of silver iones.
- the concentration of chloride iones is determined by the coefficient of conversion obtained from the calibration curves of the method (cf. Fig.3). In this case a value of 10.2 kg "1 of PCBs equivalent Aroclor 1260 was obtained.
- the watery phase is in this manner separated from the oily phase and directly transferred into a first disposable dark glass container containing a prearranged amount of solution of AgN0 3 0,1 M (500 ⁇ ).
- the suspension turns considerably cloudy; the first container is lightly shaken for a few seconds.
- the residual concentration of silver iones is determined using a selective electrode of silver iones.
- the concentration of chloride iones is determined by the coefficient of conversion obtained by using the calibration curves of the method (cf. Fig.3). In this case a value of 142 mg kg "1 of PCBs equivalent on the solution A was obtained that referred to the soil, corresponding to 468 mg kg "1 of PCBs equivalent Aroclor 1260, with a good approximation with the real concentration.
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Abstract
The process comprises the succession of the following phases: dosing of a pre-established quantity of the liquid matrix in a controlled atmosphere vial in which sodium biphenyl or sodium naphthalene is micro-dispersed in a glycol or a derivative of glycol; dosing in the vial of an extracting acid solution of KNO3; filtration of the extracting solution through a first filter with a pore diameter < 1 μm in a first container containing a pre-dosed solution of silver nitrate which causes the precipitation of the chlorides; and quantitative determination of the residual silver iones, whose quantity is correlated with the total chlorine present in the matrix.
Description
Process for the quantitative determination of total chlorine in a matrix
This invention relates to a process for the quantitative determination of the total chlorine in a matrix, possibly expressed as polychlorinated biphenyls (PCBs) equivalent, in particular in insulating liquids, oils in general, soils or metal components of apparatuses, foods, products for agriculture, in compliance with Best Available Techniques (BAT) and Best Environmental Practices (BEP) guidelines for Smart Field Test (SFT).
The PCBs can be absent (< 2 mg kg"1) in fresh insulating liquids and in oils in general, whereas - for what oils in operation used in equipment are concerned - the concentration must be below the limits prescribed by laws and local regulations (ex. <50 mg kg"1 according to Directive 96/59/EC, etc.). The inventory of the oils and the equipment containing or contaminated by PCBs, as well as their life cycle management (LCM) and the periodic monitoring with the decontamination and/or disposal of such oils and equipment is a fundamental requisite to prevent unreasonable risks for workers, public health and the environment, in compliance with the normative set of reference (Convention of Stockholm for persistent organic pollutants - POPs - of 22/5/2001 ; norms CENELEC CLC/TR 50503:2010; IEC 602960; IEC 60422; etc.).
The determination of the PCBs in a matrix requires a complex, expensive and extended process, starting with a representative sampling with a throw away kit, the shipment of the sample to an accredited laboratory operating according to specific methodologies (ex. IEC 61619, EN 12766) equipped with expensive apparatuses (ex. Gas chromatographs with ECD sensors) and specialised operators.
The well known cases of contamination by PCBs of the food chain (sausages, hams, poultry, pork meat etc. - cases occurred in Belgium in 1999 and in Ireland etc.) and the scandals deriving from the unlawful recycling of used vegetable oils, contaminated by PCBs during the recycling phases (transportation, stocking and use as an ingredient for livestock farming) dictated new requisites for quality control and traceability during all the operational phases.
Also, a wide case history exists of sites contaminated by PCBs as a result of preceding spills from equipment or accidental cases with explosions and fires and/or unlawful disposals. The identification and the reporting of these sites require a fast and effective preliminary evaluation of the concentration of PCBs in the various matrices involved, finalised toward the definition in a rapid, effective and economical way, of a map of the contamination of the site (perimeter, depth and level of contamination for the single matrices) thus planning the type and priority of corrective actions, as well as monitoring the activities for the decontamination, recovery and disposal of the various matrices involved (soil, porous concrete, metal parts) in accordance with current norms and local regulations.
The most effective, least expensive solution, not requiring considerable investments in equipment and specialised personnel, is the use of simple and rapid Field Screening Tests to quantify the concentration of total chlorine expressed as PCBs equivalent, which are scientifically validated, in accordance with what indicated by the same norms mentioned above.
Currently,, the market offers products providing the determination of total chlorine, exploiting colorimetric, electro-chemical and enzymatic methods, for example:
- kit Dexsil® (USA) designated as Clor-N-oil, i. e. field tests for the screening of PCBs in insulating oils;
-kit Dexsil® (USA) designated as Clor-N-soil, i. e, field tests for the screening of PCBs in soil;
- the apparatus by Dexsil® designated as L2000DX PCB/Chloride ANALYZER System for the quantitative determination of chlorine in insulating oils, and
- the PCBs immunoassay kit by Hach for the measurement of PCBs in soil.
The kits currently available on the market for the determination of total chlorine expressed as PCBs equivalent in oils and soil present some critical factors.
Critical factor I
The kit Clor-N-Oil is a colorimetric method having the main limitation of being unable to quantify the concentration of total chlorine in the oil, but only the compliance with a prefixed threshold value (ex. 500, 50 o 20 mg kg"1).
Critical factor II
The kit Clor-N-Oil, L 2000 uses highly toxic substances such as, for example, nickel nitrate and mercury nitrate.
Critical factor III
The kit Clor-N-Oil requires a substantial amount of oil (at least 10 ml) thus determining a corresponding amount of waste to be disposed of.
Critical factor IV
The Dexsil® L2000 is able to provide a quantification of the total chlorine with the cost of the use of a much more expensive dedicated instrument (with respect to the Clor-N-Oil) equipped with a selective electrode for chloride iones, capable of solving the limitations linked to the kit Clor-N-Oil.
Critical factor V
In the Dexsil® kits, the sodium and the naphthalene required to convert the organic chlorine into chloride is placed in two separate vials.
Critical factor VI
The kit for immunoassay by Hach, based upon enzymatic reactions, is of a purely semiquantitative nature and it can be applied to solids only and not to oils.
F.L. Benton et al.: "Quantitative Volumetric Analysis of Carbon-Bonded Halogen with
Sodium Naphthalene", Analytical Chemistry, vol. 20, no. 3, 1 March 1948, pages 269-270 XP55015068 describes an analysis method of an halogen linked to atoms of carbon (thus excluding the inorganic chlorine) based exclusively on the use of sodium naphthalene in ethereal solution of which the dispersion characteristics are not indicated. The sample containing the halogen to be analysed is weighted in a glass bulb and is placed in a separating "funnel" - i.e. a container unsuitable for field use and absolutely not comparable with a "vial" - where the sodium naphthalene solution is added, forming sodium halide. The latter is separated by adding just water three times. The watery layers are then titred potentiometrically.
Scott Hinman: "Determination of Soluble Chloride: the Volhard Titration", 9 September 2009, XP55015103 describes the Volhard method for the determination of chlorine, expressly specifying that the colloidal particles that are formed when the silver iones are added to solutions of chloride are too small to be removed by filtration.
Thus the object of this invention is to provide a process capable of overcoming the criticalities described above.
This scope is achieved thanks to a process having the characteristics described in one or more of the claims to follow.
The process of the invention presents the advantages or requiring lesser investments, as well as using not much toxic substances and a reduced amount of sample, for the quantitative determination, in particular by colorimetric and/or electro-chemical way, of the total content of chlorine - i.e. PCBs screening - in an organic liquid matrix, which could be possibly derived from a solid matrix to be analysed (soils or surfaces - wipe test).
Within this description, "total chlorine" is intended as the concentration of organic and inorganic chlorine present in the matrix sampled and measured as total chlorides.
As "PCB equivalent" is intended the concentration of PCBs as equivalent mixture of PCBs expressed as typical Aroclor 1260 obtained by the conversion of the total chlorides through
known conversion coefficients, capable of ensuring zero "false negatives" and to accept the "false positives" caused by the possible presence of other chlorinated compounds not classifiable as PCBs.
As "PCB Screening" is intended the evaluation of the total chlorine correlated to the potential mixtures of PCBs, present in the matrixes, with a result exceeding the prescribed limits, such to require a subsequent and specific quantitative determination of the PCBs, according to the above mentioned methodologies (IEC 61619, EN 12766 etc.).
As "false negatives" are intended the results indicating the absence of PCBs even when these are present in a concentration exceeding the limit of quantification of the method.
As " false positives" are intended the results indicating the presence of PCBs even when these are absent or are present in a concentration lower than the limit of quantification of the method. Such positive value can be attributed to the existence of other halogenated substances not classifiable as PCBs, with a result exceeding the prescribed limits such to require a subsequent and specific quantitative determination of the PCBs, in accordance with the above mentioned methodologies (IEC 61619, EN 12766 etc.).
As "representative sampling of liquids or solids" is intended the sampling of one or more determined amounts of liquid or solid matrix (oil or soil, for example, and in compliance with the laws and technical norms of the sector) in such a manner that the value of the concentration of PCBs determined is applicable to the entire matrix as a whole.
As "wipe test sampling" is intended the transfer, through controlled rubbing, of the PCBs from surfaces on which it has been deposited onto appropriate throw away tissues soaked with solvents (hexane, acetone or mixtures) from which it is easily extractable and quantifiable as mg of PCBs for a normalised surface (ex. 100 cm ).
As "micro dispenser" is intended a mechanical/electronic apparatus for the precise dosing of discrete and variable aliquots of titration solution.
The matrices on which the process of the invention can be done are, for example, insulating oils with mineral or synthetic base, lubricating oils, hydraulic oils, vegetable oils, natural or synthetic esters and solutions obtained from metal parts, soil and solid surfaces in general.
The quantitative determination of the total concentration of chlorine and the PCBs screening occurs preferably by colorimetric and/or potentiometric way. In particular, the process of the invention is based essentially upon a series of simple operational phase of conversion of the organic chlorine into inorganic chlorine through the reaction between 5 ml of oil (50% less with respect to the 10 ml of Clor-N-Oil, critical factor III) and a pre- dosed micro dispersion of sodium biphenyl or sodium naphthalene in a glycol or a derivative of it (normally dimethoxy ethyl ether also designated as diglyme), kept in an inert atmosphere in a sealed gastight disposable vial, in order to ensure for a long time the surprising performances in terms of limits of quantification, repeatability and reproducibility of the invention. The possibility of keeping the sodium biphenyl or naphthalene in inert atmosphere in a sealed disposable vial proved the simplification of the analytical methodology with respect to the kit Dexsil® (criticality V) since it reduces the number of parts and analytical operations. At the end of the reaction the chlorides obtained are extracted by a watery solution containing non-toxic potassium nitrate (and not mercury or nickel nitrate, cf. Critical factor II) and sulphuric or nitric acid, added to the vial after opening it. Then, the extraction solution is filtered through a 0.45 μηι nylon or teflon filter into a first container containing a pre-dosed volume of watery solution with a known concentration of silver nitrate. The products of the reaction are filtered through an additional 0.45 μηι teflon or nylon filter, into a second container for the quantification of the chlorine by a colorimetric way through titration with a 0.1 M solution of potassium thiocyanate added by a micro doser, with the presence of ferric sulphate. As an alternative, so that the sensibility of the quantification is increased, the latter can be done by electrochemical way, by a selective electrode for silver iones. In case of a colorimetric quantitative determination, at the moment the equivalent point is reached, the solution under examination turns from colourless into orange. In practice, the chlorides of such solution are caused to precipitate with an excess of silver nitrate and the residual silver iones are quantified by one of the above mentioned methods.
In case a solid matrix is examined, ex. soil, the relevant chlorinated compounds must be pre-emptively extracted by washing with a known amount of a solvent, such as for example, hexane, heptane, trimethyl pentane, acetone, ethyle ether. So, a liquid matrix is obtained, which is subject to the same process describe above.
In case a surface must be analysed, the so called wipe test, i.e. a mechanical-chemical removal of chlorinated organic compounds by using a disposable tissue soaked with hydrocarbon solvent (ex. hexane, acetone and mixtures) is used. These components are then extracted from the tissue by the addition of an hydrocarbon solvent, as for example, heptane or trimethyl pentane, obtaining a liquid matrix, which is subject to the same process described above.
As already indicated, the sodium biphenyl or naphthalene complex is specifically prepared in an appropriate sealed vial in which an oxygen and carbon dioxide-free atmosphere is ensured.
Thanks to the process of the invention, the total chlorine can be determined with high levels of repeatability a reproducibility both in the field and in laboratory, involving non- specialised personnel and without using expensive and bulky dedicated equipment, such as gas chromatographs with ECD probes (as required by complex authorisations for the presence radioactive isotope Ni 63). Thanks to this, it is possible, in particular, to measure values of total chlorine and PCBs screening between 2 through 1000 mg kg"1 (and beyond with an appropriate dilution) in the oils.
The process of the invention proved to be surprisingly as the simplest, economical and fast response under all the application scenarios, solving the critical factors described above, for the determination of total chlorine and PCBs screening in compliance with the guidelines of Best Available Techniques (BAT) and Best Environmental Practices (BEP) for Smart Field Test (SFT).
The following examples, provided without a limitative title, further illustrate the application of the process of the invention also with the help of the enclosed drawing
tables, in which:
figure 1 is a graph showing the comparison between the results obtained on exhausted mineral insulating oils applying the colorimetric technique of this invention and the gas chromatography ECD in accordance with norm IEC 61619 and EN 12766 (with error bars),
figure 2 is an example of the calibration curve usable in the method for the colorimetric determination of the invention with the concentration of the PCBs indicated as a function of the micro litres of titration solution added (potassium thiocyanate 0.05 or 0.1 M) in the typical case of an exhausted mineral oil, and
figure 3 is an example of calibration curve usable with the potentiometric determination method of the invention with concentration of PCBs Aroclor 1260 indicated as a function of the concentration of the residual silver iones, in the case of a typical exhausted mineral oil.
Example 1
In a disposable sealed vial in argon atmosphere filled with 1 ml of Na biphenyl at 20% w/w, 5 ml of oil to be analysed is poured (colour ASTM: 4, TAN: 0,706 mg OH/g sam le; cone. PCBs: 257 mg kg"' - analysis GC-ECD). The vial is sealed and vigorously shaken for about 30 seconds; the vial is reopen and 10 ml of acid extracting solution containing potassium nitrate is added, it is resealed and vigorously shaken for 2 minutes. The separation into two phases is awaited for about 10 minutes, than transfers the whole into a 20 ml disposable syringe without the piston, to the end of which a 0.45 μπι filter is placed. The watery phase is in this manner separated from the oily phase and directly transferred in a first disposable dark glass container containing a prearranged amount of solution of AgN03 0,1 M (500 μΐ). The suspension turns considerably cloudy; the first container is lightly shaken for a few seconds and the content is transferred into a 10 ml syringe without the piston to the low end of which a 0.45 μιη filter is placed. In this manner the suspension is filtered and transferred into a second 20 ml container filled with a 100 μΐ solution of indicator Fe2(S04)3; the solution turns pale-yellow. Using a micro doser, a solution of KSCN 0.1 M is added with doses of 10 μΐ at a time; gradually, a white precipitated is formed. After adding 220 μΐ, the suspension turns orange. Through the coefficient of
conversion obtained from the calibration line of the method (cf. Fig.2) it was calculated that such value corresponds to a concentration of 252 mg kg"1 of PCBs equivalent Aroclor 1260.
Example 2
In a disposable sealed vial in argon atmosphere filled with 1 ml of Na biphenyl at 20% w/w, 5 ml of oil to be analysed is poured (colour ASTM: 1.5, TAN: 0.075 rngKoiVg sample; cone. PCBs: 27 mg kg"1 - analysis GC-ECD). The vial is sealed and vigorously shaken for about 30 seconds; the vial is reopen and 10 ml of acid extracting solution containing potassium nitrate is added, it is resealed and vigorously shaken for 2 minutes. The separation into two phases is awaited for about 10 minutes, than transfers the whole into a 20 ml disposable syringe without the piston, to the end of which a 0.45 μηι filter is placed. The watery phase is in this manner separated from the oily phase and directly transferred into a first disposable dark glass container containing a prearranged amount of solution of AgNC"3 0,1 M (500 μΐ). The suspension turns imperceptibly cloudy; the first container is lightly shaken for a few seconds and the content is transferred into a 10 ml syringe without the piston to the low end of which a 0.45 μηι filter is placed. In this manner the suspension is filtered and transferred into a second 20 ml container filled with a 100 μΐ solution of indicator Fe2(S04)3; the solution turns a very pale-yellow. Using a micro doser, a solution of KSCN 0.1 M is added with doses of 10 μΐ at a time; gradually, a white precipitated is formed. After adding 420 μΐ, the suspension turns orange. Through the coefficient of conversion obtained from the calibration line of the method (cf. Fig.2) it was calculated that such value corresponds to a concentration of 34 mg kg"1 of PCBs equivalent Aroclor 1260.
Example 3
In a disposable sealed vial in argon atmosphere filled with 1 ml of Na biphenyl at 20% w/w, 5 ml of oil to be analysed is poured (colour ASTM: 4, TAN: 0.706 mg OH/g sample; cone. PCBs: 257 mg kg"1 - analysis GC-ECD). The vial is sealed and vigorously shaken for about 30 seconds; the vial is reopen and 10 ml of acid extracting solution containing
potassium nitrate is added, it is resealed and vigorously shaken for 2 minutes. The separation into two phases is awaited for about 10 minutes, than transfers the whole into a 20 ml disposable syringe without the piston, to the end of which a 0.45 μιη filter is placed. The watery phase is in this manner separated from the oily phase and directly transferred into a first disposable dark glass container containing a prearranged amount of solution of AgN03 0,1 M (500 μΐ). The suspension turns considerably cloudy; the first container is lightly shaken for a few seconds. The residual concentration of silver iones is determined using a selective electrode of silver iones. The concentration of chloride iones is determined by the coefficient of conversion obtained from the calibration curves of the method (cf. Fig.3). In this case a value of 284 kg"1 of PCBs equivalent Aroclor 1260 was obtained.
Example 4
In a disposable sealed vial in argon atmosphere filled with 1 ml of Na biphenyl at 20% w/w, 5 ml of oil to be analysed is poured (colour ASTM: 1, cone. PCBs: 9.8 mg kg"1 - analysis GC-ECD). The vial is sealed and vigorously shaken for about 30 seconds; the vial is reopen and 10 ml of acid extracting solution containing potassium nitrate is added, it is resealed and vigorously shaken for 2 minutes. The separation into two phases is awaited for about 10 minutes, than transfers the whole into a 20 ml disposable syringe without the piston, to the end of which a 0.45 μιτι filter is placed. The watery phase is in this manner separated from the oily phase and directly transferred into a first disposable dark glass container containing a prearranged amount of solution of AgN03 0,1 M (500 μΐ). The suspension turns considerably cloudy; the first container is lightly shaken for a few seconds. The residual concentration of silver iones is determined using a selective electrode of silver iones. The concentration of chloride iones is determined by the coefficient of conversion obtained from the calibration curves of the method (cf. Fig.3). In this case a value of 10.2 kg"1 of PCBs equivalent Aroclor 1260 was obtained.
Example 5
In a 250 ml glass flask, 10 g of dry soil contaminated by PCBs at 420 mg kg"' is placed, 50
ml of hexane are added and the whole is placed in an ultrasound bath for one hour. A filtration over paper is done and the solution (solution A) is collected for the subsequent quantification of the PCBs.
In a disposable sealed vial in argon atmosphere filled with 1 ml of Na biphenyl at 20% w/w, 5 ml of solution A to be analysed is poured. The vial is sealed and vigorously shaken for about 30 seconds; the vial is reopen and 10 ml of acid extracting solution containing potassium nitrate is added, it is resealed and vigorously shaken for 2 minutes. One waits about 10 minutes for the separation into two phases than transfers the whole into a 20 ml disposable syringe without the piston, to the end of which a 0.45 μηι filter is placed. The watery phase is in this manner separated from the oily phase and directly transferred into a first disposable dark glass container containing a prearranged amount of solution of AgN03 0,1 M (500 μΐ). The suspension turns considerably cloudy; the first container is lightly shaken for a few seconds. The residual concentration of silver iones is determined using a selective electrode of silver iones. The concentration of chloride iones is determined by the coefficient of conversion obtained by using the calibration curves of the method (cf. Fig.3). In this case a value of 142 mg kg"1 of PCBs equivalent on the solution A was obtained that referred to the soil, corresponding to 468 mg kg"1 of PCBs equivalent Aroclor 1260, with a good approximation with the real concentration.
Naturally, without prejudice to the principle of the invention, the details for carrying it out and the forms of implementation can widely change with respect to what described herein purely for an exemplifying title, without for this reason going out the claims area.
Claims
1. Process for the quantitative determination of the total chlorine in an organic liquid matrix, comprising the succession of the following phases:
- dosing of a pre-established quantity of the liquid matrix in a controlled atmosphere vial in which sodium biphenyl or sodium naphthalene is present micro- dispersed in a glycol or a derivative of glycol;
- dosing in the said vial of an extracting solution which is an acid solution of KN03;
- filtration of the extracting solution through a first filter with a pore diameter < 1 μιη in a first container containing a pre-dosed solution of silver nitrate which causes the precipitation of the chlorides; and
- quantitative determination of the residual silver iones, the quantity of which is correlated with the total chlorine present in said matrix.
2. Process according to claim 1, wherein said organic liquid matrix includes exhausted, fresh and in-operation oils, such as mineral and synthetic base insulating oils, lubricant oils, hydraulic oils, vegetable oils, natural and synthetic esters, fuels, solutions of organic solvents such as hexane, isooctane, acetone or mixtures thereof, used to extract PCBs from a solid matrix.
3. Process according to claim 2, wherein said solid matrix comprises soils, asphalts, concrete or porous supports, sediments, wastes, metals and/or biogenics such as biomasses, food products for humans, animal feed, fertilisers and products for agriculture.
4. Process according to any of the previous claims wherein said vial, preferably made with borosilicate glass, is equipped with gas tight sealing cap capable of keeping an inert atmosphere, preferably argon or nitrogen.
5. Process according to any of the previous claims wherein said extracting solution is an acid solution of KN03, which had been made acid by sulphuric or nitric acid, preferably in an amount comprised between 1 and 40 % in weight.
6. Process according to any of the previous claims wherein said pre-established quantity of liquid matrix is equivalent to about 5 ml.
7. Process according to any of the previous claims wherein said quantitative determination occurs through a colorimetric way.
8. Process according to claim 7, wherein said colorimetric determination occurs after filtering the content of the first container through a second filter in a second container, into which is subsequently added a solution of potassium thiocyanate, preferably 0.1 M, in the presence of ferric sulphate as indicator.
9. Process according to any of the previous claims from 1 through 6 wherein said quantitative determination occurs through a potentiometric way, preferably by a selective electrode for silver iones.
10. Process according to any of the previous claims wherein said first filter is made with teflon or nylon with pore diameter preferably equivalent to about 0.45 μπι.
11. Process according to any of the previous claims from 8 through 10 wherein said second filter is made with teflon or nylon with pore diameter < 1 μιη, and preferably equivalent to about 0.45 μπι.
12. Process according to any of the previous claims wherein said liquid matrix is directly poured into said vial.
13. Process according to any of the previous claims wherein said atmosphere controlled vial contains 1 ml of Na biphenyl.
14. Process according to any of the previous claims wherein said glycol derivative is 2- methoxyethyl ether.
15. Process according to any of the previous claims wherein said extracting solution is dosed a single time in said vial.
16. Process according to any of the previous claims wherein said controlled atmosphere vial contains Na biphenyl micro-dispersed in diglyme, in the absence of sodium naphthalene and preferably at 20% w/w.
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CN105603955A (en) * | 2015-12-18 | 2016-05-25 | 重庆三峡学院 | Residual settlement calculation method based on measured data and application |
CN110631961A (en) * | 2019-09-27 | 2019-12-31 | 深圳市市政工程总公司 | Method for determining optimal mixing amount of warm-mix agent of fiber warm-mix asphalt mixture |
CN113820445A (en) * | 2020-06-18 | 2021-12-21 | 宝山钢铁股份有限公司 | Method for detecting concentration of cold rolling circulating leveling liquid |
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CN105603955A (en) * | 2015-12-18 | 2016-05-25 | 重庆三峡学院 | Residual settlement calculation method based on measured data and application |
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CN113820445A (en) * | 2020-06-18 | 2021-12-21 | 宝山钢铁股份有限公司 | Method for detecting concentration of cold rolling circulating leveling liquid |
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