Document X8rY0jBgBg5EX37m903nezjOx
giMS -OS00.7p
ilB IN A L
PHYSICAL/CHEMICAL PROPERTIES TEST SUBSTANCE ______
($ X & -o a 7 }
caoo_>
n,.:r?
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Identity: [2-(N-Ethylperfluorooctanesulfonamido) ethyl acrylate: may also bir referred to as B1228, D-1, EtFOSEA, or FX-13. (2-Propenoic acicT, 2[ethyl[heptadecafluorooctyl)sulfonyl]amino]ethyl ester, CAS # 423-82-
5)
Remarks: Material is an amber solid.
'Cb1V*- vu UL
Remarks: Report states that sample purity is 99% or more based on information supplied by Sponsor. The purity/identity of the test substance cannot be substantiated. As presented in the report, the structural formula indicates that "purity" cannot be assigned as "99% or more". The lot number was 101.
METHOD
Water Solubility: OECD 105, Shake Flask Method
Hydrolysis as a Function of pH: OECD 111
o
Dissociation Constants in Water: OECD 112, Spectrophotometric Method i f
Partition Coefficient (1-octanol/water) by HPLC: OECD 117
%
Vapor Pressure: OECD 104, Gas Saturation Method
^ i
GLP (Y/N): Yes
^
Year completed: 1994
~r
Remarks:
'
Details from these studies can be found in one report entitled: "Determination of
Physico-chemical Properties of Sample D-1".
i J
RESULTS
Water Solubility: 0.89 mg/L at 25C
Hydrolysis as a Function of pH: At 25C the reaction rate constants of the test
substance at pH 4, 7, and 9 were 0.017, 0.020, and 0.046 day"1with half life
times of 42, 35, and 15 days, respectively. Dissociation Constants in Water: No dissociation constants of the test
substance were determined because the spectra of the test substance at different pH values did not significantly differ from one another.
Partition Coefficient: Kow > 6
Vapor Pressure: 6.0 x 10"3 Pa at 25C
epa- ots
000811810J
000432
oooaiiaioj
Remarks: The study results indicated that the test substance was composed of different components which, in some cases, yielded results different from each other.
Water solubility: It is suggested that the water solubility of each component of the test substance is different from the others. Hydrolysis as a function of pH: The chemical structure of the test substance suggests that the reaction rate of each component is similar to each other. Dissociation constants in water: The water solubility of the test substance is too low to find ionized and unionized forms of the test substance. The laboratory did not investigate its constants further by either the titration method or the conductometric method in the OECD Guideline because both methods are considered not suitable for substances with such a low solubility. However, the chemical structure of the test substance suggests that its dissociation potential is very low. Parition coefficient: The test substance was detected as ten peaks or more by HPLC. Vapor Pressure: The chemical structure of the test substance suggests that the vapor pressure of each component is different from the others.
DATA QUALITY
Water Solubility Reliability: Klimisch ranking 2. The report states a purity of the substance of "99% or more". Since the purity/identity of the test substance cannot be substantiated, the stated average solubility of the test substance is not defensible. As presented, the structural formula indicates that "purity" cannot be assigned as "99 % or more". Since the method of detection is not compound specific, and was not validated, it cannot be determined if the peaks detected in the sample chromatograms do indeed arise from the test substance.
Hydrolysis Reliability: Klimisch ranking 2. Without the purity/identity information on the test substance and compound specific analytical techniques, the experimentally determined rate constant cannot be substantiated.
Dissociation Constants in Water Reliability: Klimisch ranking 1. Potential for a compound of the given structure to ionize at any pH is low.
Octanol/Water Partition Coefficient
000433
Reliability: Klimisch ranking 3. Since the purity/identity of the test substance cannot be substantiated, the stated partition coefficient is not defensible. It was not established in this study what the retention time(s) of the test substance(s) is. The UV detector is not compound specific and it has not been definitively established that the >10 peaks assigned as belonging to the test compound are actually related to the test material. Furthermore, it has not been established that this method for determining the octanol/water partition coefficient applies to fluorochemical compounds similar in structure to the test material.
Vapor Pressure Reliability: Klimisch ranking 3. The purity/identity of the test substance cannot be substantiated. The chromatogram of the test substance has a distinctly different profile that that of the standard. It has not been established that under the conditions of the experiment the nitrogen passed over the substance has become saturated with gas phase test substance. The reference compound (benzoic acid) has a measured vapor pressure ~ 16 times that determined for the test substance. It would be appropriate to choose a reference compound with a vapor pressure closer to that determined for the test compound The lower molecular weight constituents will have a higher vapor pressure than the n=8 component.
REFERENCES________________________________________________ Study conducted at the request of Sumitomo 3M LTD by Mitsubishi Chemical Safety Institute Ltd., Yokohama, Japan
OTHER______________________________________________________ Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133
Last changed: 5/22/00
000434
M.S.I. Report No. 4B223-4B227 Determination of Physico-chemical Properties of
Sample D-l
Submitted to: SUMITOMO 3M LTD.
Prepared by: Mitsubishi Chemical Safety Institute Ltd.
February 14, 1996 (The original report was submitted on August 8, 1994)
000435
Determination of Physico-chemical Properties of Sample D-l (English version)
Study No.: 4B223-4B227 Study Title: Determination of Physico-chemical Properties of Sample D-l Sponsor: SUMITOMO 3M LTD.
This test was conducted in Yokohama Laboratory of Mitsubishi Chemical Safety Institute Ltd., 1000 Kamoshida-cho, Aoba-ku, Yokohama 227, Japan.
This report is the English version of the original, which was written in Japanese. The undersigned hereby declare that this version faithfully reflects the original report to the best of our knowledge.
Translated by
Date:__ L>_..(.K. + .-i-.f-J-.h Shiro IWAMI, M.Sc. Environmental Science Division of the Yokohama Laboratory
Approved by
Head of the Yokohama Laboratory,
000436
Testing Facility
Study No.: 4B223-4B227 Study Title: Determination of Physico-chemical Properties of Sample D-l Sponsor: SUMITOMO 3M LTD.
Testing Facility:
Yokohama Laboratory, Mitsubishi Chemical Safety Institute Ltd. ^ (M.S.I.), 1000 Kamoshida-cho, Aoba-ku, Yokohama 227, Japan (telephone: 045-963-3541) (^ThTehfeorcmomerpannaym'se:naMmitesuwbaisshci-hkaansgeeidInosntitOutcetoobfeTro1x,ic1o9l9o4g.ical and Environmental Sciences)
Facility Management:
Jun TORIYA, B.Sc. Head of the Yokohama Laboratory
Sealed date: August 8, 1994
Study Management:
Tadayoshi SHIGEOKA, Ph.D.
Sealed date: August 8, 1994
CEnhvieirfoRnemseenartaclhSScciieenncteistD, ivision of the Yokohama Laboratory
Study Director:
Takemi NAKANOME, B.Sc.
Sealed date: August 8, 1994
SEennviiorornRmeesenatarclhScSiceinecnetisDt,ivision of the Yokohama Laboratory
Experimental Scientist:
Akiko TAKEDA, M.Sc.
Sealed date: August 8, 1994
Environmental Science Division of the Yokohama Laboratory
000437
Contents
page
Abstract.............................................................................................................................5 1 Test Substance.............................................................................................................6
1.1 Identification.....................................................................................................6 1.2 Source.................................................................................................................6 2 Water Solubility [Study No. 4B223]..........................................................................7 2.1 Materials and Methods................................................................................ 7 2.2 Results and Discussion...................................................................................... 9 Tables and Figures.................................................................................................... 27 3 Hydrolysis as a function of pH [Study No. 4B224].................................................. 10 3.1 Materials and Methods......................................................................................10 3.2 Results and Discussion.......................................................................................14 Tables and Figures.................................................................................................... 35 4 Dissociation Constants in Water [Study No. 4B225].................................................16 4.1 Materials and Methods......................................................................................16 4.2 Results and Discussion.......................................................................................18 Figure......................................................................................................................... 50 5 Partition Coefficient (1-octanol/water) by HPLC Method [Study No. 4B226].......19 5.1 Materials and Methods......................................................................................19 5.2 Results and Discussion...................................................................................... 21 Figures........................................................................................................................51 6 Vapor pressure [Study No. 4B227].............................................................................22 6.1 Materials and Methods...................................................................................... 22 6.2 Results and Discussion...................................................................................... 26 Tables and Figures.................................................................................................... 53
(59 pages in all)
000438
Abstract
Study No.: Study Title: Sponsor:
4B223-4B227 Determination of Physico-chemical Properties of Sample D-l SUMITOMO 3M LTD.
1 Test Substance Name: Sample D-l Chemical name: 2et-h[Nyl-eatchryyll-aNte-perfluoroalkyl (C=l-8) sulfonylamino] Structural formula: CnF2n+iS02N(C2H5)CH2CH20C(=0)CH=CH2
n = 1-8 (n=8: approx 78 %; n - 1-7: approx. 21 %)
2 Water Solubility [Study No. 4B223] 22..12 MReestuhlotsd:s: WNoa.te1r05s"o1lu"bWilaittyeroSfothluebtielistty"su(bFsltaasnkceMweathso0d.)89 mg/L at 250C.
3 Hydrolysis as a function of pH [Study No. 4B224]
3.1 3.2
RMeestuhlotsd:s:aaonnfdd4AN29t9,oa23.t5wI52l,e5lCr'ae1'nCrd"e0)Ha.10cy5t1dio7drona, ylyr0sas,.ti0esr2eacs0spo,enacsattnfiavudnentslc0yt..oi0of4nt6hoefdtpaeHsyt1"s,uwb(tisetthsatninhcgealfaattlpipfHHe
4, 7, 4ti,m7e,
4 Dissociation Constants in Water [Study No. 4B225] 4.1 Methods:MetNhoo.d1)121" "Dissociation Constants in Water" (Spectrophotometric 3.2 Results: bstlhoiegewcnNa.i)tufeoisscetdanitsshtusleyobcsdsitaapiftneifccoeetnrrafscruooognmfgstetaohsnntestestaetohnsfatotttshhuieetbsr.stetda(sBnitscusseotucbtahisatettaidncoihcnfeefemprwoeicetneartnel tpsidHatrelutecdirtsimudrvienenerooydft
5 Partition Coefficient (1-octanol/water) by HPLC Method [Study No. 4B226]
5.1 5.2
MReestuhlotsd:s:TPehreNTfolhoorem.gitaPennsoct'w1esuvLbai"qsluPtuaeaindrcotieCftithwohrneaosmmdaaCetiotnoegeccrftaofepimdchipyeaons(ntHteenPntL(pnwCe-ao)askcMstmaenootorhrelo/mwdtho"aartenerb6),.y
High HPLC.
6 Vapor Pressure [Study No. 4B227] 66..12 MReestuhlotsd:s: NVoap. o10r4p^re"sVsuarpeoorfPtrheesstuesret sCuubrsvtaen"ce(GwaassS6a.t0urXat1io0n-3MPeathaot d2)5 C.
^ fNorumTbesetrinign oOfrgCahneimzaictiaolns for Economic Cooperation and Development (OECD) Guidelines
000439
1.1 Identification
1 Test Substance
1) Name+:
Sample D-l
Chemical namet: 2et-h[Nyl-eatchryyll-aNte-perfluoroalkyl(C = 1-8) sulfonylamino]
2) Structural formulat:CnF2n+!S02N(C^H5)CH2CH20C (=0)C H =C H
n= 1-8 (n=8: approx.
78
%;
n=l-7:
approx.
21
%)
3) Physico-chemical properties:
Solubility t :
waDcaMetetoSr:nOe:: i5inn0ssoo%lluubbollreemore
Melting pointt : 27-42 C
Boiling pointt: approx. 150C (1 mm Hg)
+ provided by the sponsor
1.2 Source
OBatcht:
Lot No. 101
2) Supplier:
Misao SHIBA, SUMITOMO 3M LTD.
3) Supplied quantity4: approx. 100 g
4) Purity4:
99 % or more
5) Appearance: amber like wax
t provided by the sponsor
000440
2 Water Solubility [Study No. 4B223]
A solution is a homogeneous mixture of different substances in a solvent. The particle sizes of the dispersed substances are of the same magnitude as molecules and ions. Therefore, the smallest volumes which can be obtained from a solution are always of uniform composition.
Solubility in water is a significant parameter because the spatial and temporal movement (mobility) of a substance is largely
determined by its solubility in water; water soluble substances gain ready access to humans and other living
organisms; the knowledge of the solubility in water is a prerequisite for testing biological
degradation and bio-accumulation in water and for other tests.
2.1 Materials and Methods
This study was conducted in accordance with the standard procedure "Water Solubility" (Flask Method) in the OECD+ Guidelines for Testing of Chemicals No. 105 (1981). This method is summarized as follows:
The test substance (Solids must be pulverized.) is dissolved in water at a temperature somewhat above the test temperature. When saturation is achieved the mixture is cooled and kept at the test temperature, stirring as long as necessary to reach equilibrium. Subsequently, mass concentration of the test substance in the aqueous solution, which must not contain any undissolved particles, is determined by a suitable analytical method.
t Organizationfor Economic Cooperation and Development
2.1.1 Reagents
ac-heteoxnaen:e:
WWaakkoo PPuurree CChheemmiiccaall IInndduussttrriieess,, LLttdd..,, gguuaarraanntteeeedd rreeaaggeenntt
2.1.2 Apparatus
icginneactnseutgcrbirhafaruttooogmrra::latsoegpraarpahto(rG: C): STHShaihtiiaimtmeccahadidCzLzuoutrdCpC.o,oorrarpptoioorranat,tiioonn,, mmmmooooddddeeeellll MSGCC-C-R1T-301A0415AB
000441
2.1.3 Test procedure
Two hundred milligrams of the test substance was dissolved in 10 mL of acetone in an Erlenmeyer glass flask. The solvent was evaporated with stirring to deposit a thin layer of the test substance onto inner surface of the flask. The residual solvent was thoroughly removed by stream of nitrogen gas . Four hundred milliliters of distilled water was added to the flask, which was then shaken at 400.2C over a 3-day period. A 50-mL aliquot of the water phase was sampled after 1, 2, and 3 days. The aliquot was subsequently shaken at 250.2C for 1 day or more to reach equilibrium of dissolution of the test substance.
The operation by the above procedure was repeated once more.
2.1.4 Analytical methods
The concentration of the test substance was measured by gas chromatography (GC). Prior to GC analysis, each equilibrated aliquot was treated as follows:
The aliquot was centrifuged at 4000 rpm (3000 X g) at 25 C. Sodium chloride, 1.2 g, was dissolved in the supernatant, to which 4 mL of -hexane was then added. They were shaken for 1 minutes and then centrifuged at 4000 rpm (3000 X g) at 25 C. The -hexane phase (supernatant) was analyzed by GC under the following conditions:
GC conditions
column: tcdienaemjrteerpcicetetiroro:arn:tuvroe:lume:
c3Senolihetpliruc0mLotm.gr5aoend3nn:zmucg1aam2Cps0toui(r.fCrpdleoo;.,wrdiae2ntrt5jieaeoctcnmett,o:orirw2n:(0iE2dlemeC0n0DLgbto/)hCmre;incd)oeltuecmtonr:C2B4P020C-W25-100,
As informed by the sponsor, the components of the test substance differ in length of the perfluoroalkyl chain (see 1.1). In fact, the test substance was detected as four major peaks with retention time of 3.8, 4.5, 5.1, and 6.0 minutes by GC under the conditions described above. Therefore, the concentration of the test substance was based on total area of the four peaks.
Q 0044*J
2.1.5 Calibration curve
Standard solutions of the test substance were prepared to make concentrations of 0, 0.2, 1.0, and 5.0 mg/L in -hexane. These standard solutions were analyzed by GC under the conditions described in 2.1.4. The total peak area of the four peaks
was calculated and plotted against the concentration of the test substance. The calibration curve yielded a straight line passing through the origin and its correlation coefficient was calculated to be 0.999 by the least square method described in Japanese Industrial Standards (JIS) Z 9041-1968.
[Figure 2.1 and Figure 2.2] At measurement of the test substance concentration, the standard solution with 1.0 mg/L was analyzed. Concentration in each test sample was calculated from ratio of total peak area for the sample to that for the standard solution.
2.1.6 Recovery
An acetone solution of the test substance was prepared to make a concentration of 483 mg/L. Two milliliters of the solution was dissolved in 1000 mL of distilled water (final concentration of the test substance: 0.97 mg/L).
Sodium chloride, 1.2 g, was dissolved in 4 mL of the water solution, to which 4 mL of n-hexane was then added. They were shaken for 1 minutes and then centrifuged at 4000 rpm (3000 Xg) at 25 C. The concentration of the test substance in the n-hexane phase (supernatant) was measured by GC under the conditions described in 2.1.4 to evaluate recovery.
[Table 2.2 and Figure 2.3] The recovery of the test substance was 94 %. The concentrations of the test substance reported below were corrected by this factor.
2.2 Results and Discussion
Average water solubility of the test substance was 0.89 mg/L at 25 C. [Table 2.1 and Figure 2.4.1 to Figure 2.4.3]
The component with GC retention time of 4.5 minutes was rather soluble in water compared with the others. Dissolution of this component at 40 C reached equilibrium within 1 day.
It is suggested that water solubility of each component of the test substance differs from one another.
000443
3 Hydrolysis as a Function of pH [Study No. 4B224]
The testing of substance for hydrolysis is relevant to their persistence. Hydrolysis is one of the most common reactions controlling abiotic degradation and is therefore one of the main degradation paths of substances in the environment.
A procedure to determine hydrolysis is important also in indicating whether other testing should be carried out on a parent compound or its hydrolysis product. It is the degradation products that are crucial.
Hydrolysis behavior needs to be examined at pH values normally found in the environment (pH 4-9) and under more acidic conditions (pH 1-2) for physiological purpose.
Surface-controlled reactions can sometimes predominate over bulk solution hydrolysis, especially in the soil environment. This may result in different degradation rates than would be predicted from this methods based upon rates in homogeneous solutions.
3.1 Materials and Methods
This study was conducted in accordance with the standard procedure "Hydrolysis as a function of pH" in the OECD Guidelines for Testing of Chemicals N o .lll (1981).
In the environment, chemicals usually occur in dilute solution, which means that water is present in large excess, and therefore, the kinetics of hydrolysis are generally pseudo-first order at fixed pH and temperature.
The hydrolysis reaction may be influenced by acidic or basic species H30+ (H+) and OH-, in which case it is referred to as specific acid or specific base catalysis.
The concentration of the test substance is determined as a function of time. The logarithms of the concentrations are plotted against time and the slope of the resulting straight line (assuming first-order or pseudo-first order behavior) gives the rate constant.
000444
3.1.1 Reagents and water
rmasmscooc-ooeddhnntiieouuooxnmmppaeono:ettchaa:hyssldssoriiruuoimmxdied:pceih:troastpeh:atJJWWKeNuu:nniaaasssckkheeaooiiildaCCaPPi uuhhTCeerreheemmseqCCiimccuhhaaieecellammICCnliicooccC.a.a.,,,oll .LLII,nnttLddddt..uud,,ss.ttrriieess,,
Ltd., Ltd.,
pbootraicssaiucimd:chloride: WJunakseoi PCuhreemCichaelmCicoa.l, ILntddu. stries, Ltd.,
gggguuuuaaaarrrraaaannnntttteeeeeeeedddd rrrreeeeaaaaggggeeeennnntttt geggxuuutaaarrrraaaannnptttueeereeeedddrrrreeeeaaaaggggeeeennnntttt
water: deionized water purified by Milli-Q
3.1.2 Apparatus
pginaHcsumcbhaerttooemrr:: atograph(GC): integrator:
STTShhaoiiia[mmteeEcqaalddueCzzicpuuotprroCeCpdnoooirrrcwappstiooitLorhraanttdta,iin.oo,nne,,lectron mmmmcaoooopddddteeeeullllreHCMGd-MC-Re1-t-301e5A04c0tASor (ECD)]
3.1.3 Test procedure
3.1.3.1 Preparation of buffer solutions Buffer solutions were prepared by the following two methods described in the
annex of the Guideline No. Ill: BCuitfrfaetre mbuixfftuerreosfoKfoCltlharokffaannddLVulbeseschhouwer
Each buffer solution of pH values 4, 7, and 9 was prepared to be 1000 mL using the following reagents:
231))) pppHHH 479:::
00 0
..11 .1
M M
m
pmmoootnanososppiuootmtaassscsihiuulmmoripcdihetor,as0tpe.h1aanMted
ba0no.dr1ic0Na.s1coiNddisauonmddiuh0my.d1rh/oy/xdsiordodexiuidme
hydroxide
The buffer solutions obtained were passed through Millipore filter of pore size 0.25 pm. The pH values of the filtrates were determined to be 4.05, 7.02, and 9.05 for nominal values of 4, 7, and 9, respectively.
3.1.3.2 Preparation of stock solution of the test substance
The test substance, 80 mg, stock solution with 40 mg/L.
was
dissolved0an0d0d4ilu4te5d
with
acetone
to
prepare
a
3.1.3.3 Preliminary test (at 50C) Fmir milliliters of the stock solution (prepared in 3.1.3.2) was added to 400 mL
each of the three buffer solutions to prepare test solutions of pH values 4, 7, and 9. The solutions thus prepared were tested under the following conditions:
I) Conditions pcteoHmn:cpeenratrtautrieo:n: ttteeessstttivnvegoslupsemelr:eio: d:
40,.470, mangd/L9 545E00rdl0.ea0nymms0Lwe.1y(iceothorCngctolaanisntsiinnfuglaosu1ks%shaackeitnogne)
II) Analytical methods The concentration of the test substance was measured by GC. Prior to GC
analysis, the test solutions were treated by the following procedure:
Sodium chloride, 128 g, was dissolved in each of the three 400-mL solutions, from which the test substance was then extracted with 100 mL of -hexane. The extraction was repeated twice more. The three extracts were combined and concentrated to 50 mL, which was then transferred into a 200-mL glass volumetric flask and filled to 200 mL with -hexane. The hexane solution was analyzed by GC under the following conditions:
GC conditions
column: tcdienaemjrteerpcicetetiroro:arn:tuvroe:lume:
3ScnEoihCtpliru0DmLom.g5aen3dn:zmug1am2Cs0oi(r.fCpdloo;.,wria2ntr5jiaeotcnmet,:oriw2n:0i2dlem0en0Lgbto/hmCre;incd)oeltuecmtonr:C2B4P020C-W25-100,
As described in 2.1.4, the concentration of the test substance was based on total area of the four peaks detected by GC (retention time: 3.6, 4.3, 4.9, and 5.8 minutes).
Ill) Recovery
000446
Four milliliters of the stock solution (prepared in 3.1.3.2) was added to 400 mL of water in an Erlenmeyer glass flask (final concentration: 0.4 mg/L). Sodium
chloride, 128 g, was dissolved in this solution, from which the test substance was
then extracted with 100 mL of -hexane. The extraction was repeated twice more.
The three extracts were combined and concentrated to 50 mL, which was then transferred into a 200-mL glass volumetric flask and filled to 200 mL with -hexane. The concentration of the test substance in the final solution was measured by GC under the conditions described in 3.1.3.3.11.
Recovery was determined to be 101 %. The concentrations of the test substance reported for this preliminary test were corrected by this factor.
[Table 3.6 and Figure 3.1]
3.1.3.4 Further investigation (at 25 C) Four milliliters of the stock solution (prepared in 3.1.3.2) was added to 400 mL
each of the three buffer solutions to prepare test solutions of pH values 4, 7, and 9. Six 5-mL aliquots from each of the test solutions were transferred into glass tubes. These solutions were examined as a function of time under the following conditions:
I) Conditions pctttteeeeoHmsssnttt:icpnvveegeonrslatupsrteameultrr:ieieoo::nd::
40235g3,l.54am.7s0d0sL,amyat0(usncg.bd2ow/eLn9iCttahinniongsh1ak%inagcetone)
II) Analytical methods The concentration of the test substance was measured by GC. Prior to GC
analysis, the test solutions were treated by the following procedure:
Sodium chloride, 1.6 g, was dissolved in the 5-mL aliquot treated in the tube. Two milliliters of -hexane was added to this solution. They were shaken for 1 minutes and then centrifuged at 3000 rpm. The -hexane phase (supernatant) was analyzed by GC as described in 3.1.3.3.
As described in 2.1.4, the concentration of the test substance was based on total area of the four peaks detected by GC (retention time: 3.6, 4.3, 4.9, and 5.8 minutes).
000447
Ill)
Recovery Four milliliters of the stock
solution
(prepared
in 3.1.3.2)
was
added
to 400 mL
of water in an Erlenmeyer glass flask (the final concentration: 0.4 mg/L). Sodium
chloride, 1.6 g, was dissolved in a 5-mL sample of this solution, to which two milliljters of -hexane was then added. They were shaken for 1 minutes and then centrifuged at 3000 rpm. The -hexane phase (supernatant) was analyzed by GC under the conditions described in 3.1.3.3.
Recovery was determined to be 95 %. The concentrations of the test substance reported for this further investigation were corrected by this factor.
[Table 3.7 and Figure 3.3]
3.1.3.5 Calibration curve The calibration curve prepared in 2.1.5 (Determination of Water Solubility)
was used. [Figure 2.1 and Figure 2.2]
At measurement of the test substance concentration, the standard solution of the test substance with 1.0 mg/L was analyzed. Concentration in each test sample was calculated from ratio of total peak area for the sample to that for the standard solution.
3.1.3.6 Calculations Residual percent of the test substance was calculated as follows:
rt = lOOCQ/Qo)
where rt: residual percent of the test substance after "t" days Q : concentration of the test substance after "t" days (mg/L) C^: initial concentration of the test substance (0.4 mg/L)
Assuming that the logarithms of the residual concentrations are first order as a function of time, their reaction rate constants were calculated as follows:
k = t-1 In (100/rt)
where k: reaction rate constant of the test substance (day1)
Using the average of these rate constants, half life time of the test substance was calculated as follows:
ti/2 = k-1 In 2
where half life time of the test substance (days)
000448
3.2 Results and Discussion
1) Preliminary test
After 5 days at 50C the residual percents of the test substance at pH 4, 7, and 9 were 76, 76, and 52, respectively.
[Table 3.5 and Figure 3.2] On the basis of the results, it is suggested that the test substance is transformed at least by 24 %. Relating to the preliminary test result, there is the following description in the OECD Guideline: If less than 10 per cent of the reaction is observed after 5 days (tj/2 > 1 year), the chemical is considered hydrolytically stable and no additional testing is required. Therefore, we decided to perform the further investigation described below.
2) Further investigation
At 25 C the reaction rate constants of the test substance at pH 4, 7, and 9 were 0.017, 0.020, and 0.046 day1 with half life time of 42, 35, and 15 days, respectively.
[Table 3.1 to Table 3.4 and Figure 3.4] The chemical structure of the test substance (shown in 2.2) suggests that the reaction rate of each component is similar to each other.
000449
4 Dissociation Constants in Water [Study No. 4B225]
The dissociation of a chemical in water is of importance in assessing its impact upon the environment. It governs the form of the substance which in turn determines its behavior and transport. It may affect the adsorption of the chemical on soils and sediments and adsorption into biological cells.
4.1 Materials and Methods
This study was conducted in accordance with the standard procedure "Dissociation Constants in Water" (Spectrophotometric Method) in the OECD Guidelines for Testing of Chemicals No. 112 (1981). General summary of this method is as follows:
A wavelength is found where the ionized and unionized forms of the compound have appreciably different extinction coefficients. The UV-visible absorption spectrum is obtained from solutions of constant concentration under a pH condition where the substance is essentially unionized and fully ionized and at several intermediate pH's. This may be done, either by adding increments of concentrated acid (base) to a relatively large volume of a solution of the compound in a multicomponent buffer, initially at high (low) pH, or by adding equal volumes of a stock solution of the compound in e.g. water, methanol, to constant volumes of various buffer solutions covering the desired pH range. From the pH and absorbance values at the chosen wavelength, a sufficient number of values for the pKa is calculated using data from at least 5 pH's where the compound is at least 10 per cent and less than 90 per cent ionized.
4.1.1 Reagents and water
0m.1eth//ahnyodl:rochloric acid: 0.1 //sodium hydroxide: water:
DKJKueiinssi((hshoddeiiniiddilliaauuzCettCCeehdddehhmweettoommaict00iieacc..rlaa00llC1w1CCoa/Ns./oo,w..dw,,LiisitLLtttdhhittl.ddl,wwe..,,daa.tteerrgrreeuaappaggrrriieeaoonnnrrtttettffeoooodrruurssttiieeetta))rragatteiinootnn
4.1.2 Apparatus
UV-visible spectrophotometer: Shimadzu Corporation, Model UV-260
000450
4.1.3 Test procedure
4.1.3.1 Preparation of stock solution of the test substance A stock solution of the test substance with 80 mg/L in methanol was prepared
using 20.0 mg of the substance. 4.1.3.2 Preparation of test solutions
For measurement of UV-visible spectra of the test substance, three solutions of the test substance were prepared as follows: 1) Acid solution of the test substance
Two milliliters of the stock solution (prepared in 4.1.3.1.) and 2.4 mL of 0.01 N hydrochloric acid were transferred into a 200-mL glass volumetric flask, which was then filled to 200 mL with water, (final concentration of the test substance: 0.8 mg/L) 2) Alkaline solution of the test substance
Two milliliters of the stock solution and 2.4 mL of 0.01 N sodium hydroxide were transferred into a 200-mL glass volumetric flask, which was then filled to 200 mL with water, (final concentration of the test substance: 0.8 mg/L) 3) Neutral solution of the test substance
Two milliliters of the stock solution was transferred into a 200-mL glass volumetric flask, which was then filled to 200 mL with water, (final concentration of the test substance: 0.8 mg/L) 4.1.3.3 Measurement of UV-visible spectrum
The UV-visible spectra of the test substance in the solutions of three different pH values were measured with the apparatus shown in 4.1.2.
000451
4.2 Results and Discussion
No dissociation constants of the test substance were determined because the spectra of the test substance at different pH did not significantly differ from one another.
[Figure 4.1] The water solubility of the test substance is too low to find an ionized and unionized forms of the test substance. We did not investigate its constants further by either "Titration Method" or "Conductometric Method" in the OECD Guideline because the both methods are considered not suitable for the substance having such a low solubility (0.89 mg/L, reported in 2.2). But the chemical structure of the test substance (shown in 1.1.2) suggests that its dissociation potential is very low.
0004S2
5 Partition Coefficient (1-octanol/water) by HPLC Method [Study No. 4B226]
The partition coefficient (P) is defined as the ratio of the equilibrium concentrations of a dissolved substance in a two-phase system consisting of two largely immiscible solvents. In case of 1-octariol and water,
^00453
Pow = Co / Cw
where Pow: 1-octanol/water partition coefficient Co: concentration in 1-octanol phase Cw: concentration in water phase
The partition coefficient being the quotient of two concentrations is usually given in the form of its logarithm to base ten (log Pow).
Pow is a key parameter in studies of the environmental fate of chemical substances. A highly-significant relationship between the Pow of substances and their bioaccumulation in fish has been shown. It has also been shown that Pow is a useful parameter in the prediction of adsorption on soil and sediments and for establishing quantitative structure-activity relationships for a wide range of biological effects.
5.1 Materials and Methods
This study was conducted in accordance with the standard procedure "Partition Coefficient (n-octanol/water), High Performance Liquid Chromatography (HPLC) Method" in the OECD Guidelines for Testing of Chemicals No. 117(1989). Principle of this method is as follows:
HPLC is performed on analytical columns packed with a commercially available solid phase containing long hydrocarbon chains (e.g. Cg, Cjg) chemically bound onto silica.
Chemicals injected onto such a column move along it by partitioning between the mobile solvent phase and the hydrocarbon stationary phase. The chemicals are retained in proportion to their hydrocarbon-water partition coefficient, with water soluble chemicals eluted first and oil-soluble chemicals last. This enables the relationship between the retention time on a reverse-phase column and the 1-octanol/water partition coefficient to be established.
5.1.1 Reference compounds
As reference compounds whose Pow values are well known, we selected five substances: methyl benzoate, bromobenzene, diphenyl, dibenzyl, and DDT. In addition, thiourea was used for determination of the dead time. A mixture of the six substances was prepared in acetonitrile.
5.1.2 Correlation between retention time and Pow
The mixture of the reference compounds (shown in 5.1.1) was analyzed by high performance liquid chromatography (HPLC) under the conditions described below:
HPLC conditions column: mwtfeloamowvbpeiellreeraantpetguh:trhaes::e:
22aG1c51.L0e04tomSn.C6ncmL(iiCte/rmnqilcgeien/mscw.hImaentmecir..i,dc=aI.,nlle72yr55tbs/02oil5muOnm(dDv/oSivnn-)2tloensgiltihca)
The HPLC retention time of the reference compounds were corrected as follows:
Rt = Rt' - Rto
where Rt: R t': Rto:
corrected retention time of the compound (minutes) retention time of the compound (minutes) retention time of thiourea (minutes)
Correlation equation between the corrected retention time of the five compounds and their corresponding Pow was computed by the least square method, resulting in the following equation:
log Pow = 5.274 log Rt - 0.0219 (r = 0.973) [Figure 5.1 and Figure 5.2]
5.1.3 Retention time of the test substance
A mixture of the test substance and thiourea was prepared in acetonitrile. The mixture was analyzed by HPLC under the conditions described in 5.1.2. Based on the chromatogram, retention time (Rt1, minutes) were determined for components of the test substance.
000454
5.2 Results and Discussion
The test substance was detected as ten peaks or more by HPLC. The corrected retention time (Rt) of the main component was determined to be 29.245 minutes, while that of DDT (Log Pow is reported to be 6.20.) was 13.263 minutes. Based on the correlation equation shown in 5.1.2, the log Pow value of the main component was more than 6.
[Figure 5.2]
000455
6 Vapor pressure [Study No. 4B227]
The environmental relevance of vapor pressure is accounted for by the following reasons:
The vapor pressure gives an indication of the probability of the phase transitions, liquid/gas and solid/gas.
The vapor pressure, together with the solubility in water, is the major auxiliary variable for calculating the volatility of a substance from an aqueous solution.
Vapor pressure is thus a significant factor for predicting atmospheric concentrations.
The vapor pressure of a substance can furthermore be useful as a basis for deciding whether or not a photochemically induced degradation study (in the homogeneous gas phase or in an absorbed phase) is necessary.
6.1 Materials and Methods
This study was conducted in accordance with the standard procedure "Vapor Pressure Curve" (Gas Saturation Method) in the OECD Guidelines for Testing of Chemicals No. 104 (1981). This method is summarized as follows:
A stream of inert carrier gas (nitrogen gas) is passed over the substance in such a way that it becomes saturated with vapor of the substance and the vapor is then collected in a trap adsorbent. Measurement of the amount of material transported by a known amount of carrier gas is used to calculate the vapor pressure at a given temperature.
6.1.1 Reagents
acetonitrile: Wako Pure Chemical Industries, Ltd., reagent for HPLC
adsorbent: GL Sciences Inc.,
Tenax GC, 60-80 mesh
000456
6.1.2 Apparatus
saturator column: adsorbent column: gfgdlalaoastwsascphmbrroeoeactmdeer:sa:stoogr:raph:
SSSSISuhhhiibcbiiihmmnaa11tit22aaaaagSddmmaSSezzwcmimcuueiiaeieCCdiinnC..ooottddiiorrff..Cppr,,iicpcooo11orr.TT55a,areae00ttLiictcooimmhhtonndnnnmm,,.oo,,llooiinnggmm1myylleemooonnLLdddggmtteeedttdllhlh..i,N,GCn -WCdRi-aK31mA4-IAeCter
6.1.3 Vapor pressure measuring apparatus
For measurement of vapor pressure of the test substance, an apparatus shown in Figure 6.5 was assembled and set in a room air-conditioned at 251 C.
[Figure 6.5]
The glass beads coated with the test substance were packed into the saturator column up to 7 cm in length. Nitrogen gas, kept at a constant flow rate by the pressure controller and the flow gauge, was introduced to this column.
The nitrogen gas saturated with vapor of the test substance was delivered to the Tenax GC-packed column to trap the test substance. Total amount of the nitrogen gas which passed through this trap column was measured by the flow meter.
Preparation of saturator column 1) Ten milligrams of the test substance was dissolved in 10 mL of acetonitrile in a 100-mL round bottom glass flask.
2) Eight milliliters of glass beads was added into the flask. The solvent was removed by rotary evaporation. The residual solvent was thoroughly eliminated with a vacuum pump at room temperature. (The test substance was thus coated onto the glass beads.)
3) The glass beads coated with the test substance was packed into the saturator column up to 7 cm in length. Both open sides of the column were held by quartz glass wool, which was then incorporated in the vapor pressure measuring apparatus.
000457
nitrogen gas 1) Nitrogen gas was delivered into the vapor pressure measuring apparatus for 70 hours. Total volume of the carrier gas was measured with the flow meter and determined to be 1.017 m3. (average flow rate: 242 mL/min)
2) The total volume of the gas was corrected as follows:
V = Vr [(273/T)(760-P) / 760]1/2
where V : total gas volume corrected (m3)
Vr: amount of the gas measured by the flow meter (1.017 m3)
T: temperature of the nitrogen gas (298 K) P: praensdsuartethdeiffaebrseonrcbeebr-eptawcekeendactotlhuemfnlo(w0.4memtemr Hg) The total volume of the carrier was thus corrected by factors of the temperature and pressure difference, resulting in 0.973 m3. Adsorbent column 1) Eight milliliters of the adsorbent (Tenax GC) was packed into the absorbent column. Both open sides of the column were retained with quartz glass wool. The column thus prepared was connected to the saturator column. 2) The test substance trapped by the Tenax GC was desorbed by the procedure described in 6.1.4.
6.1.4 Analytical methods
The test substance trapped by the adsorbent was desorbed as follows: 1) The adsorbent packed in the column was transferred into a glass filter. The
inside of the vacant column was rinsed with 20 mL of acetonitrile, which was then transferred in the glass filter. The rinse of the Tenax GC was repeated twice more with 20 mL and 10 mL each of acetonitrile. 2) The three filtrates were combined and transferred into a 50-mL volumetric glass flask, which was then filled to 50 mL with acetonitrile. An aliquot of the solution was diluted 50 fold in volume. 3) The concentration of the test substance in the final solution was measured by GC under the following conditions:
000458
GC conditions
column: ctdienaemjrteerpcicetetiroro:arn:tuvroe:lume:
c3SnEoihCtpliru0DmLom.g5aend3nz1mug2amC0so(ir.fCpdloo,.,wrian2trj5iaeotcmnet,:oriw2n02idl0eme0nLgbto/Chmre,indc)oetleucmtonr
CBP20-W25-100, 240 C
Calibration curve Standard solutions of the test substance were prepared to make concentrations of
0, 0.25, 0.5, and 1.0 mg/L in acetonitrile. They were analyzed by GC under the above conditions. A calibration curve prepared by the method described in 2.1.5 generated a straight line which crosses the origin and its correlation coefficient was calculated to be 0.999.
[Figure 6.1 and Figure 6.2]
At measurement of the test substance concentration, the standard solution with 1.0 mg/L was analyzed. Concentration in each test sample was calculated from ratio of total peak area for the sample to that for the standard solution.
Desorption efficiency (Recovery) Desorption efficiency of the test substance from Tenax GC was determined
according to the following procedure:
1) Twenty five milliliters of the solution of the test substance widi 1 mg/L in acetonitrile (mass of the test substance: 25 pg) was added to 4 mL of the adsorbent in a 50-mL round bottom glass flask. The solvent was removed by rotary evaporation to adsorb the test substance onto the Tenax GC.
2) The test substance adsorbed on the Tenax GC was recovered by the desorption procedure described above (except that the substance was extracted with 10, 10, and 5 mL of acetonitrile and the filtrates were transferred into 25-mL volumetric glass flask, which was then filled to 25 mL). The concentration of the test substance in the final solution was measured by GC to evaluate desorption efficiency.
The desorption efficiency was determined to be 97 %. For measurement of vapor
pressure, the concentration of the test substance was corrected by this factor.
0004.^9
[Table 6.3 and Figure 6.3]
6.1.5 Calculation of vapor pressure
Vapor pressure of the test substance was calculated as follows:
P = (W/MXRT/V)
wherPe: vapor pressure (Pa)
WM::
amount of the test substance trapped (g) molecular weight of the test substance (g mole"*)
VTR:::
gas constant (8.31 Pa m3 mole-1 K'l) total volume of the carrier gas corrected (m3) temperature (K)
6.2 Results and Discussion
Vapor pressure of the test substance was 6.0 X 10-3 pa [Table 6.1 to Table 6.2, and Figure 6.4]
But the chemical structure of the test substance (shown in 1.1.2) suggests that vapor pressure of each component is different from one another.
Vapor pressure of benzoic acid (a reference substance in the OECD Guideline) was 0.10 Pa (24 C) under the conditions employed in this study.
0004S0
Table 2.1 Calculation of concentration of the test substance dissolved in w ater
Measurement No. 1 time at 40 C, days
12
3
cone, in Std., mg/L peak area, pV- sec
Std. test solution concentration factor
A
1. 01
1.01
1.01
B 2589644
2717449
2732276
q 2030738
2414771
2230296
D 1 11
cone, of the substance, mg/L
E
Calculation equation E = A(C /B)( 1/D )(1/0 .9 4)
0. 84
0.95
0.88
Measurement No. 2 time at 40 C, days
123
cone. in.Std., m g/L ; peak area, fjW- sec
Std. test solution concentration factor
A
1.01
1.01
1.01
B 2589644
2717449
2732276
C 2115067
2319263
2293546
D 111
cone, of the substance, mg/L
E
0.88
0.92
Calculation equation E = AC C /B)C l/D )(1 /0 .9 4 )
average water solubility:
000461
0 .89ng/ 1
0.90
-Table 2.2 Calculation of recovery
cone, of the substance added, mg/L cone, in Std., mg/L peak area, juV -sec
Std. test solution concentration factor
A 0.97 B 1.01
C 2723221 D 2456907 E1
cone, of the substance recovered, mg/L
recovery
(X) F
Calculation equation F=BCD/C)( 1/E)C100/A)
0.91 94
000462
Figure 2.1 Calibration curve of the test substance
Curve F i t t i n g [Least Square Method]
Input Data
Concentrt ion No . X (mg/ 1)
10 2 0.20163 1.008 4 5.04
Peak Area Y( U Vsec)
0 550784 2758732 13119948
Y = 5.0483X104 + 2.5966X106 XX1 r = 0.99995
X 1000000
C a libration Curve
Figure 2.2 GC chromatograms of the test substance -- for calibration curve --
Std. Ong/1
Std. 0 . 202mg/1
CCurOO*
^
lo
rs.
I________
u<'1J
Std. 1 . 008g/1
V.
o
S td. 5.04fflg/l
c o I co o o-. CC`
CO `0 fv .
Zl T
:o 17-, TT
r r uo fs. o 0
z- CO
uo
O
Hi
0f>- Si
rCO K-
*:X UJ
r fs. 'C* co co t c .. cd co a- co :
'oC>'
or f . UO CO '' U
<x c . rs uo x* c CO
u > '.0 "1" CO --*
CT-.
'T UO UO UO
co co
UJ cb CO CO '.*J CO J
zz ^ :> co -Z' co o - u:
,-H C rs uo
c:
<hx-
.' co t uo uo r
000464
< co co
uo
T--
Ci
Figure 2.3 GC chromatograms of the test substance . -- for recovery--
Std. 1.008mg/l
test solution
TOTAL
00046S
Figure 2.4.1 GC chromatograms of the test substance " for measurement of concentration in water (after 1 day at 4 0 C)-~
Std. I - 008mg/l
TOTAL
test solution n= 1
CO**
UO
'H COt.7V. .-'..'AjO
'>V.
m7 \
-O'-
.
> I=-
<x IxJ
r , ,-r, u CO
7` CO
Ct! <1
f-. f-.
'-7T`*
rv. r-..
ri7s*..
CO
CO CO K 7%
T-.
UO
C'J CO
>2 co uo co cj r -. fv . * r r < O '7'* C
:*' co -a- uo uo r. :%
h-
h-
' co co -T uo r .
te st solution
n=2
ri-..r-'. T-.. JS
jo
'*`>K>it uo '*`fs.'7-
si c0 uo z ,
u i *: Z' UO uo a: r . UO CO N. :I c 0 7* T'
. ho Z*
'r C'J
J CO In. K CO f
:
r-.
r-s.
t
r-^ 3
UO 7-
*'. r
i
' co t uo uo r.. :
co co t uo *. r-.
00046S
Figure 2.4 .2 GC chromatograms of the test substance -- for measurement of concentration in water (after 2 days at 40 C )--
Std. 1 008rag/ 1
ru -a* ".'
test solution n= 1
"r*..
hIrT.*r r .
i*Trv-,.'Il_J
I H_A-
IO *.'
te s t solution n=2
'J T IT.' f'--.
000467
Figure 2.4.3 GC chromatograms of the test substance -- for measurement of concentration in water (after 3 days at 4 0 C)--
Std. 1 . 0 0 8 n g / l
-co tr irt
te st solution n= 1
te st solution n=2
0 4 S 8
Table 3 Calculations of reaction rate constant and half life time of the test substance (Table 3.1-Table 3.3}
Table 3.1 (pH 4 at 25C )
tim e , days (t)
residual percent rate constant,
of the substance, d a y'1
m g /L (C)
(k)
5
89.7
0.022
8
87.3
0.017
15
77.0
0.017
19
76.8
0.014
26
68.3
0.015
33
62.1
0.014
average rate constant 0. 017day~ half life tim e C11 ^ a ) 42 days
calculation equations
k = l/ t X In 100/c 11/ 2 =1/k X In 2
Tabic 3. (pH 9 at 25C )
tim e, days (t)
2 5 8 12 15 19
residual percent of the substance, m g /L (C)
rate constant, d ay'1 (k)
92.4 78.4
69.0 57.1 50.2 37.7
0.040 0.049
0.046 0.047 0.046 0.051
average rate constant 0 . 0 4 6 d a y -1
11^ 2
15 days
Table 3.2 (pH 7 at 25C )
tim e , days (t)
residual percent of the substance, m g /L (C)
rate constant, d a y'1 (k)
5 8 15 . 19 26 33
88.6 86.9 74.1 69.5 59.9 53.8
0.024 0.018 0.020 0.019 0.020 0.019
average rate constant 0 . 0 2 0 d a y ' '
t j /2
35 days
000469
Table 3.4 Calculations of residual concentration of the test substance -- for Further investigation (at 2 5 .0 0 .2 C ) --
tim e, days pH
29
4 57
9
4 87
9
12 9
4 15 7
9
4 19 7
9
4 26 7
4 33 7
peak area /V* sec
test Std solution BC
cone, in residual te st soln. percent
D
2889193 2523765 0.371 92.4
2951466 2951466 2951466
2502799 2473261 2186759
0.361 0.356 0.315
89.7 88.6 78.4
2968192 2968192 2968192
2449526 2439536 1936885
0.351 0.350 0.278
87.3 86.9 69.0
2939623 1585436 0.229 57. 1
2871668 2871668 2871668
2089210 2011015 1361482
0.309 0.298 0.202
77.0 74.1 50.2
2871088 2871088 2871088
2084603 1886031 1022942
0.309 0.279 0.152
76.8 69.5 37.7
2962788 1912723 2962788 1676378
0.275 0.241
68.3 59.9
2928913 1718699 2928913 1490039
0.250 0.216
62.1 53.8
co nce ntra tion o f the standard solution (A): 1.01 m g/L
co nce ntra tion fa c to r (E):
2.5
initial concentration of the test substance(F): 0.40 2 mg/L
reco very(G ):
95 %
calculation equation:
D = A ( C / D ) * E '1 * F- 1(1 0 0/ G )*1 00
000470
Table 3.5 Calculations of residual concentration of the test substance -- for Preliminary test (after 5 days at 5 0 .0 0.1 C) --
pH 4
pH 7
pH 9
initial concentration of the test substance, mg/L
A
0.402
0.402
0.402
after 5 days cone. in.Std.y mg/L peak area, //V *se c Std. te st solution concentration factor cone, in .the te st solution
B 1.00
1.00
1.00
C 3022269 D 1867539 E2
0.306
3022269 1876183
2 0.307
3022269 1264465
2 0.207
residual percent o f the te st substance
F 76
calculation equation
F = B (D /C )(l/E)(l/*K l/I.01)l00
76
52
000471
Table 3.6 Calculation of recovery -- for Preliminary test --
cone, of the test substance added, mg/L
cone. in Std., mg/L
peak area, /A /*se c Std. te s t solution
concentration factor
A 0.402 B 1.00
C 2977220 D 2420272 E2
cone, of the test substance recovered, mg/L
recovery, %
F
calculation equation F =B(D/C)(1/E)(1/A)100
0.406 101
Table
3.7 --
fCo ralFcuulrathtieorn inovf erseticgoavteioryn
-
-
cone, of the te st substance added, mg/L
cone. In StdJ, mg/L peak area, //V *se c
Std.
testsolution
concentration factor
A 0.402 B 1.01
C 2782217 D 2639636 E 2.5
cone, of the test substance recovered, mg/L
recovery, %
F
calculation equation F =B(D/C)(1/E)(1/A)100
0.383 95
000472
Figure 3.1 GC chromatograms of the test substance -- for recovery in Preliminary test --
S t d . (1. Omg/jg)
Ld
<X
(. *;>j
i.-r-. cr% r\. oj
'r '."'j >?j <*:z:-< oo:<j
r?'< * r-
te stso lu tio n
IjJ
C.
r-. i.t* tv. rv
ijj 13
lit
r--. *z* u* i!'
>j -7- r-OJ U"' '7*. .'J
r-
000473
Figure 3.2 GC chromatograms of the test substance -- for measurement of concentration in water in Preliminary test
S t d . ( 1 . Omg/ j2 )
PH 4
r--.
i .
tr i
Oi I
I-- SC
PI-1 7
PH 9
is.
OJ
,J> k l
oj
u-ox-a-
,v/
)
I-- <X
000474
SC
bJ fX*
TJ-
J x*..
ajvioU1 ox-..*-
<x
r-.. :u ::
fs. 'r
tz> '-i rus'. :
a
i-
oj *i*.
Figure 3.3 GC chromatograms of the test substance -- for recovery in Further investigation --
Std. 1.01mg/l
test .solution
TOTAL
000475
Figure 3.4 GC chromatograms of the test substance
-- for measurement of concentration in water
in Further investigation --
[1] after 2 days
Std. l.Olng/l
pH 9
--- "
-T. U".' 'if
Ld IT.* CO CO CO > T
u ' CO Z' O'- : CO
x n-. CC' -T
'.'J
< rj-
r-.
r
*:o h : -d-
ir.<
C'J
IjJ cu C-J CU u
xz
co -rf oj i* >
.J
`C> CO iT*. CO c :
CO T rr UO > o
Ci.
000476
Figure 3.4 (continued)
Std. 1.01 ms/1
[2] after 5 days
pH 4
pH 7
pH 9
000477
Figure 3.4 (continued)
Std. l.Olmg/1
[3] after 8 days
pH 4
TOTAL
pH 7
pH 9
00047S
Figure 3.4 (continued)
[4] after 12 days
Std. l.Olng/1
pH 9
0004*79
=oc
MO TIME AREA 111 ID M 0
1 3.5 4
5434 1 v
ii
4 . 7 5
1? 6 8 O6 V
4 . S3 3
1 3 6 2 fa55 II
4'
5 . 6 S7
4 1 6 6 1 4 C*|V|
TOTAL 0 1!015
000480
PKH0
T IME
A R l A ilK !DilC
3.6 OS
330O V
C 4 .108 337
r, 4 .3
35866
4
4 .03
1O 1O 48 4
c
5.8 17
50845 SV
--- Q-.--97--- ---- 1r.An 5--
TOTAL
PKHO
TIM E
A R E A MK
-4-------- O-.-17-g---------- i~r<++-
c o .5 o c 73 196 V
3 4 .32?
32929? v
v4 4.9
13333 92
C" 5 .7?
580734 SV
IDHO
TOTAL
2884962
0rC+1L O --
B
f-r-6 I
CTCnCQTsOC. oo3 r3c(CD+L'
ui
Q)
n"is Ol
? KM
TIME
AREA MK IDMO
4------------3 . 1 1 7 -- -------- r 8-g-102 O, ,cj .cj 5 9 ? ? 9
3
4 . 67
169135
4
4.812
1444165
c 5 .6 5 416131 3
TOTAL
2G99453
Figure 3.4 (continued)
Std. l.Olng/1
[6] after 19 days
pH 4
s/
'IO
<z Q<1T
TC'J iino
fNiT7*P-<-i
C'J "*
-tf" *Ti.nT|
Ii1111111iil
--c.so>r OJ
I
LJ T\. rs. n. co
21
0\ "T f vH 20
-J
- lo CO O' fv. <r
H-
.
I--
CO *3 - 'T LO
Ci
1--
CJ CO xj-
PH 7
Ltj0Oum r0tnJ
.'W> uhi1V'lW<crofij
O P
2C > > > >
Lo<1Jr
ccrCuuTo'oJ
*CUI-OT"H-H>irO--cT~soJ-t
v-t crceira*
co *Cc--Co*'
FL2--1J-i
Pcmno. co
Ccc-auOu*
iC0-oiT5-.
cifvou. in
<V_-h--ZxJ-'
pH 9
000481
Pi
cu co t tn
Figure 3.4 (continued)
[7] after 2 6 days
Std. l.Olug/1
pH 4
TIME AREA 1K IDHC
PH 7
OJ - OJ
j'.rvjrf's
,w" -*
<x 'X' 7* )Z, .3 I.J IN. T T j in.
C tf. o j O J O J
CO
<x
- T Z' Z* **<
ii*
U".' Z'
ro Vii*
UJ i;i*i OJ OJ
zz
- V -J- <T>
__J
*-- IO co <;o
<1
1--
.
1--
CO T
UO o
F-
_ OJ CO -*
000482
Figure 3.4 (continued)
[8] after 3 3 days
Std. 1 .0 lig/1
pH 4
pH 7
000483
Figure 4.1 UV spectrum of the te st substance in a cid ic, n eu tra l, and alkaline s o lu tio n s concentration of the test substance 0. 8mg/ i
0004S4
Figure 5.1 Correlation between HPLC retention time and Pow of the. reference compounds
Curve F i t t i n g [Least Square Method]
In p u t Data
No . 43521
log Rt 00001.....968318215216335
log Pow 43622.....8719216290
Y = - 2 . I 91 9 X i 0 " 2 + r = 0.97258
5 . I 282 X X]
X1
log Pow
000485
Figure 5.2 HPLC chromatograms of the reference compounds and the test substance
l_c R 2J0.-I
1yin* o
IG0'
%N
rM1 OQ'*
-i di;i -
*0
I!iIJ.00
of D- I.02 . D
reference com pounds
G10O** 0o--
Pea!234SG1'.X
Get 2G4.T..G38inG03e377 11925...129300340
PTDDVVVy pe CDVMVV
IO
W0 .i0d7tGh 00000.....223I10725I04G57
HQ-
--------
20
T ir.fj ;m i n .
1A1125023r11e437564a2B339....07Se2443
thiourea
-anber.oTtmtyof beennzxoeante^ts.
diphenyl
dibDeDnTzyl
Rt-Rlo
2. 266 4.230 6.502 9. 567 13. 263
I O
lo Rt
0. 355
0. 626
0.813
0l..
981 123
log Pow
2.12 2. 99 3.76 4.81 6. 20
l.C 0 2 1 0 . *1
*1 S il . 0 0
o f D - l . 0 3 . I)
0004S6
O*
10 T t ir.t:; \ tu2i0n . >
3O
d0
Pea11k3254G718091X
Re 2l21152792525.T.......G1553534i450n306404S324e258 223 817 ...378527920
TPUype
V'J VV DV BV VV BV BV VV VV \VJ
W00000000000....i.......0212347445d2G5955713585l1G9519762h29
A25r5e59a930..9099
!
2
371
e94
...
G48
434
2S33175576G7918....84213838
thiourea
RL-Rln
3.511 4.922 6. 869 9. 671 13.812 19. 929 23. 675 24.726 26. 089 29. 245
log 111
0. 545 0. 692 0. 837 0. 985 1. 140 1. 299 1.374 1.393 1.416 1.466
log Row
2. 77 3.75 4.27 5. 03 5. 82 6. 64 7.02 7. 12 7. 24 7. 50
Table 6.1 Calculation of vapor pressure
trapped te s t substance (corrected mass), g m olecular w eight of the test substance gas constant, P a*m 3*m oIe-i *K -i corrected total volume of the carrier gas, m 3 temperature, K
W 1.47X 1 0 '3 M 625 R 8.31 V 0.973 T 298
vapor pressure, Pa
calculation equations P = CW/M)(RT/V)
P 6. OX IO' 3
Table 6.2 Calculation of mass of the trapped test substance
cone... iniStd.; mg/L peak area, p V *se c
Std. test solution cone, in'the test solution, mg/L final volume, mL dilution factor
A 1.006
B 2489067 C 1412087
0.571 D 50 E 50
trapped te st substance as m easured mass, g
as corrected mass, g
1.43 X 10"3 W 1.47X 10'3
calculation equation =A (C /B )E (D /1000)(1/0.97) (1/1000)
000487
Table 6.3 Calculation of desorption efficiency
cone, of the test substance added, mg/L
cone, in Std., mg/L
peak area, ^ V * s e c
Std. te st solution
final volume, mL
A 0.02515 B . 1.006
C 2451409 D 2372240
25
cone, of the test substance recovered, mg/L
desorption efficiency, %
E F
0.02434 97
calculation equations E = B(D/C)(25/1000)
F ==( E / A ) 100
000488
Figure 6.1 Calibration curve of the test substance
Curve F i t t i n g [Least Square Method]
Input Data No . C o n c e nXt r(mtg/i o1n)
4321 001...5200503230
YP( eUakV As ereca) 21 426 730 542 617 889 7600
Y = - 9 . 1 5 0 6 X 1 0 3 + 2 . 4 7 4 0 X 1 0 6 X X1 r = 0.99997
X 1000000
Cal ibrat ion Curve
000489
Figure 6.2 GC chromatograms of the test substance -- for calibration curve --
Std. Omg/
Std. 0. 25mg/
C;Or 0" '~-C.r' o I,
C*J U"i C'J o |
-'J >:r-.
0
-- J <Z'
| v-<
I
AK
49
IJ^
'-X
:v>
Std. 0. 50mg/^
000430
K j-.
1V> F'-tri'*.' r - . V '- C T t is. OZ* O' . .
l__M ___
X C'J C'j 1 `L>
.J Tf' <:j >:*. 1 u j
iV 'T\ r-.. Z* '7 1
a
. H CV *'
7'
C'J .j'*" t *:'.
Co *'J
U 1 0'.' r-.. O' n-. f-. ...J
i--i r - V Z' >7 - < x l-- 1--
:o T 0'.' 0- > o
Figure 6.3 GC chromatograms of the test substance -- for desorption efficiency --
S t d . (1. Orag/ i )
test solution
44
000491
Figure 6 .4 GC chromatograms of the test substance for measurement of mass of the trapped test substance
iStd. (1. Omg/ )
X
co oj
' r
UY CO
Li"' '-tx
UY '.ill
cv'.Jo-
:-j -- Vr-L._'
te s t.s o lu tio n
Id
X
r-. co .* :o
''
XX
j r-..
...j. .,f
x CO IjJ i]T'. iT`. r--..
iY UY
CD
X
co OJ CO -r
T-.
UY :o c o OJ O "1'
co 'T
C'J
1,1 C'J CO f--.
r f- co r-.. rj- . O'-
..J
J-
d' UY UY
--
-- oj :.X
I--
X
Id
cj ::*
r>t-..-
v-:
r--.
u"
oj
co
iYX.'.
-
cj
--ol1
co
oj
co
co
-.r co
UY
iT--. *JL'
r
i..d b
oj
'-d oj * bY -- *
*: *. f\. -t '7'.
: : co -'i- u". uy
:u co
uy
00049?
CQ
C
CD
z
6.5 Vapor pressure measuring apparatus
000493
