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‚Methods of Soil Analysis‘, Vol 1 and 2, American Society of Agronomy, Madison, WI, 1982.
Green R.E., and Yamane V.K., (1970) ‘Precision in pesticide adsorption measurements’.
Green R.E., and Yamane V.K., (1970) ‚Precision in pesticide adsorption measurements‘.
Proc., 34, 353-354.
Proc., 34, 353–354.
‘Effect of ratio of soil to water on adsorption of linuron and atrazine’.
(1970), ‚Effect of ratio of soil to water on adsorption of linuron and atrazine‘.
Soil Sci., p. 109-138.
Soil Sci., 109–138.
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Boesten, J.J.T.I, ‚Influence of soil/liquid ratio on the experimental error of sorption coefficients in pesticide/soil system‘.
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Bastide J., Cantier J.M., et Coste C., (1980) ‘Comportement de substances herbicides dans le sol en fonction de leur structure chimique’.
Bastide J., Cantier J.M., et Coste C., (1980), ‚Comportement de substances herbicides dans le sol en fonction de leur structure chimique‘. Weed Res.
Brown D.S., and Flagg E.W., (1981) ‘Empirical prediction of organic pollutants sorption in natural sediments’.
Brown D.S., and Flagg E.W., (1981), ‚Empirical prediction of organic pollutants sorption in natural sediments‘.
Environ.Qual., 10(3), p. 382-386.
Environ.Qual., 10(3), 382–386.
Chiou C.T., Porter P.E., and Schmedding D.W., (1983) ‘Partition equilibria of non-ionic organic compounds between soil organic matter and water’.
Chiou C.T., Porter P.E., and Schmedding D.W., (1983), ‚Partition equilibria of non-ionic organic compounds between soil organic matter and water‘.
Technol., 17(4), p. 227-231.
Technol., 17(4), 227–231.
Gerstl Z., and Mingelgrin U., (1984) ‘Sorption of organic substances by soils and sediments’.
Gerstl Z., and Mingelgrin U., (1984), ‚Sorption of organic substances by soils and sediments‘.
Health, B19 (3), p. 297-312.
Health, B19 (3), 297–312.
Vowles P.D., and Mantoura R.F.C., (1987), ‘Sediment-water partition coefficient and HPLC retention factors of aromatic hydrocarbons’.
Vowles P.D., and Mantoura R.F.C., (1987), ‚Sediment-water partition coefficient and HPLC retention factors of aromatic hydrocarbons‘.
Chemosphere, 16(1), p. 109-116.
Chemosphere, 16(1), 109–116.
‘Relationship between water solubility, soil sorption, octanol-water partitioning and concentration of chemicals in the biota’ in Aquatic Toxicology (eds J.G.
‚Relationship between water solubility, soil sorption, octanol-water partitioning and concentration of chemicals in the biota‘ in Aquatic Toxicology (eds J.G.
Eaton, et al.), p. 78-115, ASTM STP 707, Philadelphia.
Eaton, et al.), pp.78–115, ASTM STP 707, Philadelphia.
Chiou C.T., Peters L.J., and Freed V.H., (1979) ‘A physical concept of soil-water equilibria for non-ionic organic compounds’.
Chiou C.T., Peters L.J., and Freed V.H., (1979), ‚A physical concept of soil-water equilibria for non-ionic organic compounds‘.
Science, Vol. 206, p. 831-832.
Science, Vol. 206, 831–832.
Hassett J.J., Banwart W.I., Wood S.G., and Means J.C., (1981) ‘Sorption of/-Naphtol: implications concerning the limits of hydrophobic sorption’.
Hassett J.J., Banwart W.I., Wood S.G., and Means J.C., (1981), ‚Sorption of/-Naphtol: implications concerning the limits of hydrophobic sorption‘.
Karickhoff S.W., (1981), ‘Semi-empirical estimation of sorption of hydrophobic pollutants on natural sediments and soils’.
Karickhoff S.W., (1981), ‚Semi-empirical estimation of sorption of hydrophobic pollutants on natural sediments and soils‘.
Chemosphere, Vol. 10(8), p. 833-846.
Chemosphere, Vol. 10(8), 833–846.
Moreale A., van Bladel R., (1981) ‘Adsorption de 13 herbicides et insecticides par le sol.
Moreale A., van Bladel R., (1981), ‚Adsorption de 13 herbicides et insecticides par le sol.
Relation solubilité — reactivité.
Relation solubilité – reactivité‘.
Revue de l'Agric., 34 (4), p. 319-322.
Revue de l'Agric., 34 (4), 319–322.
‘Comparison of screening methods for the determination/estimation of adsorption coefficients on soil’.
(1996), ‚Comparison of screening methods for the determination/estimation of adsorption coefficients on soil‘.
Chemosphere, 32(12), p. 2493-2504.
Chemosphere, 32(12), 2493–2504.
Kördel W., Kotthoff G., Müller M. (1995) ‘HPLC — screening method for the determination of the adsorption coefficient on soil — results of a ring test’.
Kördel W., Kotthoff G., Müller M. (1995), ‚HPLC – screening method for the determination of the adsorption coefficient on soil – results of a ring test‘.
Chemosphere 30 (7), p. 1373-1384.
Chemosphere 30 (7), 1373–1384.
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Kördel W., Stutte J., Kotthoff G. (1993), ‚HPLC – screening method for the determination of the adsorption coefficient on soil – comparison of different stationary phases‘.
Chemosphere 27 (12), p. 2341-2352.
Chemosphere 27 (12), 2341–2352.
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Hance, R.J., (1967), ‚The speed of Attainment of Sorption Equilibria in Some Systems Involving Herbicides‘.
Weed Research, Vol. 7, p. 29-36.
Weed Research, Vol. 7, str. 29–36.
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(1984), ‚Potential pesticide contamination of groundwater from agricultural uses‘, in Treatment and Disposal of Pesticide Wastes, pp. 297–325, ACS Symp.
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Giles C.H., (1970), ‚Interpretation and use of sorption isotherms‘ in Sorption and Transport Processes in Soils.
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Soc., p. 3973-93.
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Caractéristiques générales de l'adsorption‘.
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Bedbur E., (1996), ‚Anomalies in the Freundlich equation‘, Proc.
COST 66 Workshop, Pesticides in soil and the environment, 13-15 May 1996, Stratford-upon-Avon, U.K.
COST 66 Workshop, Pesticides in soil and the environment, 13–15 May 1996, Stratford-upon-Avon, U.K.
Guth, J.A., (1985) ‘Adsorption/desorption’, in Joint International Symposium, Physicochemical Properties and their Role in Environmental Hazard Assessment, July 1-3, Canterbury, UK.
Guth, J.A., (1985), ‚Adsorption/desorption‘, in Joint International Symposium, Physicochemical Properties and their Role in Environmental Hazard Assessment, July 1–3, Canterbury, UK.
Testing scheme
Shema preskusa
Set up of a suitable analytical method
Priprava primerne analitske metode Predhodna študija
Available?
Kinetika adsorpcije
No further test
Desorpcijske izoterme
Prerequisite
Na razpolago?
Preliminary study
Ni nadaljnjega preskusa
2 Soils
2 tipa tal
Determination of equilibrium time
Določitev časa, potrebnega za vzpostavitev ravnotežja
Check for adsorption on the vessel surface
Preverjanje adsorpcije na površino posode
Check for the stability by means of parental mass balance
Preverjanje stabilnosti s pomočjo masne bilance izhodiščne snovi Je ravnotežni konstanten nivo vzpostavljen? Da Da Ne 5 tipov tal
Tier 1 Equilibrium plateau is achieved? Yes Adsorption kinetics Tier 2
Kd*(msoil/V0) > 0,3 (posredna metoda: merjenje izgubljanja snovi iz raztopine)
If mass balance < 90%, test substance is unstable in the time scale of the test. The test test can continue by analysing both phases (soil and aqueous solution). 5 Soils
Kd*(msoil/V0) > 0,1 (neposredna metoda: merjenje obeh faz)
Kd*(msoi/V0) > 0.3 (indirect method : measurement of solution depletion)
Če je masna bilanca < 90%, je preskusna snov v času trajanja preskusa nestabilna. Preskus se lahko nadaljuje z analiziranjem obeh faz (tal in vodne raztopine) kot je ustrezno
Kd*(msoi/V0) > 0.1 (direct method : measurement of both phases)
Stopnja 2
as appropriate
Stopnja 1
Tier 3 Adsorption isotherms
Stopnja 3
INFLUENCE OF ACCURACY OF ANALYTICAL METHOD AND CONCENTRATION CHANGE ON ACCURACY OF ADSORPTION RESULTS
VPLIV TOČNOSTI ANALITSKE METODE IN SPREMEMBE KONCENTRACIJE NA TOČNOST REZULTATOV ADSORPCIJE
From the following table (84) it becomes obvious that when the difference between the initial mass (m0 = 110 μg) and equilibrium mass (maq
Iz nasleduje tabele (84) je očitno, da pri zelo majhni razhki med začetno maso (mo = 110 μg) in ravnotežno maso (maq
= 100 μg) of the test substance in the solution is very small, an error of 5 % in the measurement of equilibrium concentration results in an error of 50 % in the calculation of the mass of the substance adsorbed in soil (ms
= 100 μg) preskusne snoví v raztopini. 5 % napaka v merjenju ravnotežne koncentracije povzroči 50 % napako pri ízračunavanja mase soovi, adsorbirane na tla (ms
and of 52,4 % in the calculation of the Kd.
and of 52,4 % napako pri izračunavanju Kd.
Amount of soil
Količina tal msoil
Volume of solution
Prostornina raztopine
FOR A = 9 %
ZA A = 9 %
= 110 μg or C0 = 1,100 μg/cm3
= 110 μg or C0= 1,100 μg/cm3
true value
Dejanska vrednost
FOR A = 55 %
ZA A = 55 %
m0= 110 μg or C0 = 1,100 μg/cm3
m0= 110 μg or C0= 1,100 μg/cm3
FOR A = 99 %
ZA A = 99 %
mass of the test substance in the soil phase at equilibrium, μg;
masa preskusne snovi v talni fazi ob ravnotežju, μg;
mass of the test substance in the aqueous phase at equilibrium, μg;
masa preskusne snoví vodni fazi ob ravnotežju, μg;
content of the test substance in the soil phase at equilibrium, μg g-1;
vsebnost preskisne snovi v talni fazi ob ravnotežju, μg g-1;
mass concentration of the test substance in the aqueous phase at equilibrium, μg cm-3;
masna konceutracija preskusne snovi v vodili fazi ob ravnotežju. μg cm-3;
R analytical error in the determination of the maq
R analitska napaka pri dolocanju maq
R‡ calculated error due to the analytical error R.
R‡ izračunana napaka zaradi analitske napake R.
ESTIMATION TECHNIQUES FOR KD
TEHNIKE OCENJEVANJA Kd
Estimation techniques permit prediction of Kd based on correlations with, for example, Pow values (12)(39)(63-68), water solubility data (12)(19)(21)(39)(68-73), or polarity data derived by application of HPLC on reversed phase (74-76).
Tehnike ocenjevanja omogočajo napovedovanje Kd na podlagi korelacij z, na primer, vrednostmi Pow (12) (39) (63–68), podatki o topnosti v vodi (12) (19) (21) (39) (68–73) ali podatki o polarnosti, dobljenimi z uporabo HPLC z obrnjeno fazo (74–76).
As shown in Tables 1 and 2, is the Koc or Kom that are calculated from these equations and then, indirectly, the Kd from the equations:
Kakor je prikazano v tabelah 1 in 2, se iz teh enačb izračuna Koc ali Kom in nato, posredno, Kd iz enačb:
The concept of these correlations is based on two assumptions: (1) it is the organic matter of the soil that mainly influences the adsorption of a substance; and (2) the interactions involved are mainly non-polar.
Koncept teh korelacij temelji na dveh predpostavkah: (1) na adsorpcijo snovi v največji meri vplivajo organske snovi v tleh; in (2) vpletene interakcije so večinoma nepolarne.
As a result, these correlations: (1) are not, or are only to some extent, applicable to polar substances, and (2) are not applicable in cases where the organic matter content of the soil is very small (12).
Zaradi tega te korelacije: (1) niso uporabne za polarne snovi ali so zanje uporabne samo do neke mere, in (2) niso uporabne v primerih, ko je vsebnost organskih snovi v tleh zelo majhna (12).
In addition, although satisfactory correlations have been found between Pow and adsorption (19), the same cannot be said for the relationship between water solubility and extent of adsorption (19)(21); so far the studies are very contradictory.
Poleg tega, čeprav so bile med Pow in adsorpcijo sicer ugotovljene zadovoljive korelacije, tega ni mogoče trditi za odnos med topnostjo v vodi in obsegom adsorpcije (19) (21); dosedanje študije si zelo nasprotujejo.
Some examples of correlations between the adsorption coefficient and the octanol-water partition coefficient, as well as water solubility are given in Tables 1 and 2, respectively.
Nekaj primerov korelacije med adsorpcijskim koeficientom in porazdelitvenim koeficientom oktanol/voda ter topnostjo v vodi je navedenih v tabeli 1 oziroma 2.
Examples of correlations between the adsorption distribution coefficient and the octanol-water partition coefficient; for further examples (12) (68).
Primeri korelacij med adsorpcij skim porazdelitvenimim koeficientom in porazdelitvenim koeficientom oktanol/voda; za dodatne primere glej (12) (68)
Correlations
Korelacije
Substituted ureas
Substituirane sečnine
Aromatic chlorinated
Aromatske klorirane
Various pesticides
Razni pesticidi
Aromatic hydrocarbons
Aromatski ogljikovodiki
Examples of correlations between the adsorption distribution coefficient and water solubility; for further examples see (68) (69).
Primeri korelacij med adsorpcijskim porazdelitvenim koeficientom in topnostjo v vodi; za dodatne primere glej (68) (69)
Aliphatic, aromatic chlorinated substances
Alifatske, aromatske klorirane snovi
log Kom = (4,040 +/- 0,038) - (0,557 +/- 0,012) log Sw
log Kom = (4,040 +/– 0,038) – (0,557 +/– 0,012) log Sw
logKoc = 4,273 - 0,686 log Sw
logKoc = 4,273 – 0,686 log Sw
Cyclic, aliphatic aromatic substances
Ciklične, alifatske aromatske snovi
logKoc = -1,405 - 0,921 log Sw-0,00953 (mp-25)
logKoc = -1,405 – 0,921 log Sw-0,00953 (mp-25)
Various compounds
Razne spojine
CALCULATIONS FOR DEFINING THE CENTRIFUGATION CONDITIONS
IZRAČUNI ZA DOLOČITEV POGOJEV CENTRIFUGIRANJA
The centrifugation time is given by the following formula, assuming spherical particles:
Čas centrifugiranja se izračuna po naslednji enačbi ob predpostavki kroglastih delcev:
For simplification purposes, all parameters are described in non-SI units (g, cm).
Za poenostavitev so vsi parametri opisani z enotami, ki niso enote SI (g, cm).
ω = rotational speed (=2 π rpm/60), rad s-1
ω hitrost vrtenja (=2 π rpm/60), rad s-1;
rpm = revolutions per minute
rpm vrtljaji na minuto;
η = viscosity of solution, g s-1 cm-1
η viskoznost raztopine, g s-1 cm-1;
= particle radius, cm
polmer delcev, cm;
= soil density, g cm-3
gostota tal, g cm-3;
= solution density, g cm-3
gostota raztopine, g cm-3;
= distance from the centre of centrifuge rotor to top of solution in centrifuge tube, cm
razdalja od središča rotorja centrifuge do gladine raztopine v centrifugirki, cm;
= distance from the centre of centrifuge rotor to bottom in centrifuge tube, cm
razdalja od središča rotorja centrifuge do dna centrifugirke, cm;
= length of the soil/solution mixture in the centrifuge tube, cm.
dolžina zmesi tla/raztopina v centrifugirki, cm.
In general practice, double the calculated times is used to ensure complete separation.
V splošni praksi se uporabljajo dvakratni izračunani časi za zagotovitev popolne ločitve.
The equation (1) can be simplified further if we consider the viscosity (η) and the density (ρaq) of the solution as equal to the viscosity and density of water at 25 oC; thus, η = 8,95 × 10-3 g s-1 cm-1 and ρaq = 1,0 g. cm-3.
Enačbo (1) je mogoče še bolj poenostaviti, če predpostavimo, da sta viskoznost (η) in gostota (ρaq) raztopine enaki viskoznosti in gostoti vode pri 25 oC; torej, η = 8,95 × 10-3g s-1cm-1 IN ρaq = 1,0 g.cm-3.
Then, the centrifugation time is given by the equation (2):
Nato se izračuna čas centrifugiranja po enačbi (2):