CA1069331A - Method of treating plant growth substrates - Google Patents
Method of treating plant growth substratesInfo
- Publication number
- CA1069331A CA1069331A CA231,624A CA231624A CA1069331A CA 1069331 A CA1069331 A CA 1069331A CA 231624 A CA231624 A CA 231624A CA 1069331 A CA1069331 A CA 1069331A
- Authority
- CA
- Canada
- Prior art keywords
- chelate
- substrate
- exchange resin
- forming
- heavy metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000008635 plant growth Effects 0.000 title abstract 3
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 18
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 16
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002689 soil Substances 0.000 claims description 7
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 159000000003 magnesium salts Chemical group 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- NYRAVIYBIHCEGB-UHFFFAOYSA-N [K].[Ca] Chemical compound [K].[Ca] NYRAVIYBIHCEGB-UHFFFAOYSA-N 0.000 claims 1
- 239000007859 condensation product Substances 0.000 claims 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 244000211187 Lepidium sativum Species 0.000 description 5
- 235000007849 Lepidium sativum Nutrition 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 240000006108 Allium ampeloprasum Species 0.000 description 2
- 235000005254 Allium ampeloprasum Nutrition 0.000 description 2
- 240000007087 Apium graveolens Species 0.000 description 2
- 244000000626 Daucus carota Species 0.000 description 2
- 235000002767 Daucus carota Nutrition 0.000 description 2
- 240000004713 Pisum sativum Species 0.000 description 2
- 235000010582 Pisum sativum Nutrition 0.000 description 2
- 244000088415 Raphanus sativus Species 0.000 description 2
- 241000208422 Rhododendron Species 0.000 description 2
- 235000009337 Spinacia oleracea Nutrition 0.000 description 2
- 244000300264 Spinacia oleracea Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 240000000785 Tagetes erecta Species 0.000 description 2
- 235000012311 Tagetes erecta Nutrition 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 159000000007 calcium salts Chemical group 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000003864 humus Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000208 phytotoxic Toxicity 0.000 description 2
- 230000000885 phytotoxic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- VVWOYFCFAMRFJT-UHFFFAOYSA-N 2-[amino-(1-amino-2,2-dicarboxyethyl)sulfanylmethyl]propanedioic acid Chemical compound OC(=O)C(C(O)=O)C(N)SC(N)C(C(O)=O)C(O)=O VVWOYFCFAMRFJT-UHFFFAOYSA-N 0.000 description 1
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 240000002022 Anthriscus cerefolium Species 0.000 description 1
- 235000007258 Anthriscus cerefolium Nutrition 0.000 description 1
- 235000002764 Apium graveolens Nutrition 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- 241001332183 Brassica oleracea var. sabauda Species 0.000 description 1
- 235000004214 Brassica oleracea var. sabauda Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000298479 Cichorium intybus Species 0.000 description 1
- 235000007542 Cichorium intybus Nutrition 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000208822 Lactuca Species 0.000 description 1
- 235000003228 Lactuca sativa Nutrition 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 240000009164 Petroselinum crispum Species 0.000 description 1
- 235000002770 Petroselinum crispum Nutrition 0.000 description 1
- 244000062780 Petroselinum sativum Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000019057 Raphanus caudatus Nutrition 0.000 description 1
- 235000011380 Raphanus sativus Nutrition 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 241000109329 Rosa xanthina Species 0.000 description 1
- 244000292071 Scorzonera hispanica Species 0.000 description 1
- 235000018704 Scorzonera hispanica Nutrition 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000294925 Tragopogon dubius Species 0.000 description 1
- 235000004478 Tragopogon dubius Nutrition 0.000 description 1
- 235000012363 Tragopogon porrifolius Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000001387 apium graveolens Substances 0.000 description 1
- -1 bis-(dicarboxy-methyl-aminomethyl) ether Chemical compound 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006225 natural substrate Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 235000011197 perejil Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000020079 raki Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Cultivation Of Plants (AREA)
- Fertilizers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
METHOD OF TREATING PLANT GROWTH SUBSTRATES
Abstract of the Disclosure A method of treating a heavy metal containing plant growth supporting substrate to reduce damage to the plants or to reduce heavy metal residues in plants grown on said substrate, said method comprising mixing a chelate-forming ion exchange resin with said substrate in an amount to provide from 0.2 to 10 equivalents of chelate-forming group per equivalent of heavy metal in the substrate.
Le A 15 878-Ca
Abstract of the Disclosure A method of treating a heavy metal containing plant growth supporting substrate to reduce damage to the plants or to reduce heavy metal residues in plants grown on said substrate, said method comprising mixing a chelate-forming ion exchange resin with said substrate in an amount to provide from 0.2 to 10 equivalents of chelate-forming group per equivalent of heavy metal in the substrate.
Le A 15 878-Ca
Description
1~6~ 3~
The invention relates to methods of treating substrates capable of supporting the gro~th of plants to reduce damage to, and/or to reduce heavy metal residues in, plants growing on the substrates.
In recent times there is an increasing number of cases in which naturally occurring substrates, because of their high content of heavy metals, can no longer be used for growing plants since the natural growth of the plants is impaired or prevented, or since the plants exhibit excessively high contents of heavy metals, for example lead, which are toxic or phytotoxic ----to humans (see, for example, P. Sorauer in "Handbuch der Pflanzenkrankheiten"
("Handbook of Plant Diseases"), volume I, 2nd instalment, 1969, pages 203-204, 221-222, 306-309 and 392-394). Thus, for example, difficulties arose in growing azaleas, since the azalea cuttings did not root in the conventional conifer soil which was used for growing cuttings and which, as was shown by subsequent analysis, contained 200 ppm of lead, 100 ppm of copper and 200 ppm of zinc.
It has now been found that the damage caused to plants by heavy metals which are phytotoxic or toxic to humans, and/or the residues in plants grown on substrates containing these metals, can be reduced or even avoided completely, if chelate-forming ion exchange resins are added to these sub-strates.
According to the present invention, therefore, there is provided a method of treating a substrate capable of supporting the growth of a plant to reduce damage to and/or to reduce heavy metal residues in plants grown on the substrate comprising incorporating from about 0.2 to about 10 equivalent of an insoluble chelate-forming ion-exchange resin into the substrate per equivalent of heavy metal to be fixed.
1~69331 The inv~ntion al~o provide~ a ~ne-thod of reducin~ heavy r~et~l residues in a plant grown on a ~ubstrate con~ainin~ a he~vy metal comprisin~ ~rowing the plant on a substrate treated by rl method according to the preceding para~raph.
The chelate-forming ion exchange resins to be used according to the in~ention are known. They, and the various processes for their preparation, are described in detail in, for example, R. Hering "Chelatbildende Ionen-austauscher" ("Chelate-forming Ion Exchangers"), Akademie-Verlag, Berlin, 1967. The chelate-forming ion exchangers can be based on a great variety o~ resin matrices. Thus, the resin structures may be, for example, condensation resins, such as are obtained by condensation of aliphatic and/or aromatic amines with epichlorohydrin and/or ~ormaldehyde.
The preparation of such condensation resins is known and is de~cribed7 for example, in R, Griesbaoh "Austausch-Adsorption in Theorie und Praxis" ("Exch~nge Adsorption in Theory and Practice"), Akademie-Verlag, Berlin, 1957, pages 56 to 62.
Preferably, howe~er, the matrices on which the chelate-forming ion exohange resins are ba~ed are macroporou~ or microporous copolymer~ of monovinyl compounds, for example styrene, ~inyl-toluene or v~nyln~phthalene, and polyvlinyl compounds, such as divinylbenzene or trivinylbenzene, which are prepared in a manner which is in itsel~ known, for example in accordance with the method~ diaclo9ed in German Patent Specification 1,045,102 (macroporous pJlymexs)or R.Griesbach "Austausch-Ad~orption in Theorie und Pr~is" ~xchange Adsorption in m eory and Practice"), Akademie ~erlag, Berlin, 1957, pages 56 to 62 Le A 15 878 - 3 -1~)6~33~
(microporous polymers) and into which the functional chelate-forming groups are introduced in a manner which is in itself known.
Chelate-forming groups which have proved particularly suitable are the groups derived from N-(poly)-alkanecarboxylic acids, for example N-(poly)-acetic acids, such as nitrilotriacetic acid, ethylenediamine-tetraacetic acid, diethylenetriamine-pentaacetic acid, N-~-hydroxyethyl-ethylenediamine-triacetic acid, cyclohexane-trans-1,2-diamino-tetraacetic acid, ethylene-diamine-N,N'-di-(o hydroxyphenyl)-acetic acid, N,N'-di-~-hydroxyethyl-ethylenediamine-diacetic acid, bis-(dicarboxy-methyl-aminomethyl) ether or bis-(dicarboxymethyl-aminomethyl) sulphide and especially from iminodiacetic acid.
The chelate-forming ion exchangers can be employed in variously charged ~orms. Depending on the composition of the substrate to be treated, it is advisable to use the exchangers in the H form or in their salt ~orm, pre~erably the form of the potassium9 calcium or magnesium salt.
Furthermore, the use of mixtures of the variously charged forms can under certain circumstances be advantageous. The ion exchangers to be used according to the in~-ention can be used in the form of granules, in bead form or in powder form.
For use in granule form or bead form, chelate-forming ion exchangers with a macroporous matrix are particularly suitable.
The ion exchangers to be used according to the invent-ion are in general employed by adding the chelate-forming ion exchangers to the substrates to be treated by raki~g or digging-over and ensuring that the substrate and the ion exchanger are mixed as intimately as possible with one another.
~e A 15 ~7~ - 4 . , The amount in which the ion exchangers to be used according to the invention are employed per m3 of substrate depends essentially on the heavy metal content of the sub-strate. In general, the resins are employed in an amount such that 0.2-10, preferably 0.5-2, equivalents of chelate-forming group in the ion exchanger are present per 1 equivalent of heavy metal to be fixed. The optimum amount can also be determined, for example, empirically by the so-called cress test. This test is carried out by growing cress on a subst~ate containing heavy metal and determining what amount of chelate-forming ion exchange resin, when added, restores normal growth of the young plants.
The substrates to be treated according to the invention can be either natural substrates such as humus soils, peaty soils, sandy soils, loam soils or clay soils, or syn-thetic substrates) for example substrates based on polyure-thane.
The followin~ Examples i:lustrate the invention.
:~xaTDple s 1,250 g/m3 o~ an ion exchange resin containing imino-diacetic acid groups (in the calcium salt form; matrix: macro-porous polystyrene crosslinked with 8% of divinylbenzene;
iminodiacetic acid group equivalent: 3.8 milliequivalents/g) were worked into five different substrates having a raised content of toxic heavy metalsO Cress was sown after 14 days on the substrates thus obtained and after 12 days the rooting of the young plants was examined; the following results were obtained (t~e rooting was assessed in terms o~ ratings 0 to 6, wherein 0 = no rooting and 6 = normal rooting).
e ~ 15 ~8 - 5 -., , , ~, . .. . ...
106~331 Example No Suh~t~ate ~ IV V
Control _ Cuntreated substrate) 1 1 0 2 0 1 Treated substrate 5.5 5.5 4 5.5 5.5 l~hen the ion exchange resin was employed in the magnesium salt form ~A) or in the form of the calcium-magnesium salt ~B~, instead of in the calcium-salt form, an equivalen~ improvement of the substrate was achieved, as can be seen from the table which follows Example No. Substrate I II III IV V
~ Control 1 1 0 2 0
The invention relates to methods of treating substrates capable of supporting the gro~th of plants to reduce damage to, and/or to reduce heavy metal residues in, plants growing on the substrates.
In recent times there is an increasing number of cases in which naturally occurring substrates, because of their high content of heavy metals, can no longer be used for growing plants since the natural growth of the plants is impaired or prevented, or since the plants exhibit excessively high contents of heavy metals, for example lead, which are toxic or phytotoxic ----to humans (see, for example, P. Sorauer in "Handbuch der Pflanzenkrankheiten"
("Handbook of Plant Diseases"), volume I, 2nd instalment, 1969, pages 203-204, 221-222, 306-309 and 392-394). Thus, for example, difficulties arose in growing azaleas, since the azalea cuttings did not root in the conventional conifer soil which was used for growing cuttings and which, as was shown by subsequent analysis, contained 200 ppm of lead, 100 ppm of copper and 200 ppm of zinc.
It has now been found that the damage caused to plants by heavy metals which are phytotoxic or toxic to humans, and/or the residues in plants grown on substrates containing these metals, can be reduced or even avoided completely, if chelate-forming ion exchange resins are added to these sub-strates.
According to the present invention, therefore, there is provided a method of treating a substrate capable of supporting the growth of a plant to reduce damage to and/or to reduce heavy metal residues in plants grown on the substrate comprising incorporating from about 0.2 to about 10 equivalent of an insoluble chelate-forming ion-exchange resin into the substrate per equivalent of heavy metal to be fixed.
1~69331 The inv~ntion al~o provide~ a ~ne-thod of reducin~ heavy r~et~l residues in a plant grown on a ~ubstrate con~ainin~ a he~vy metal comprisin~ ~rowing the plant on a substrate treated by rl method according to the preceding para~raph.
The chelate-forming ion exchange resins to be used according to the in~ention are known. They, and the various processes for their preparation, are described in detail in, for example, R. Hering "Chelatbildende Ionen-austauscher" ("Chelate-forming Ion Exchangers"), Akademie-Verlag, Berlin, 1967. The chelate-forming ion exchangers can be based on a great variety o~ resin matrices. Thus, the resin structures may be, for example, condensation resins, such as are obtained by condensation of aliphatic and/or aromatic amines with epichlorohydrin and/or ~ormaldehyde.
The preparation of such condensation resins is known and is de~cribed7 for example, in R, Griesbaoh "Austausch-Adsorption in Theorie und Praxis" ("Exch~nge Adsorption in Theory and Practice"), Akademie-Verlag, Berlin, 1957, pages 56 to 62.
Preferably, howe~er, the matrices on which the chelate-forming ion exohange resins are ba~ed are macroporou~ or microporous copolymer~ of monovinyl compounds, for example styrene, ~inyl-toluene or v~nyln~phthalene, and polyvlinyl compounds, such as divinylbenzene or trivinylbenzene, which are prepared in a manner which is in itsel~ known, for example in accordance with the method~ diaclo9ed in German Patent Specification 1,045,102 (macroporous pJlymexs)or R.Griesbach "Austausch-Ad~orption in Theorie und Pr~is" ~xchange Adsorption in m eory and Practice"), Akademie ~erlag, Berlin, 1957, pages 56 to 62 Le A 15 878 - 3 -1~)6~33~
(microporous polymers) and into which the functional chelate-forming groups are introduced in a manner which is in itself known.
Chelate-forming groups which have proved particularly suitable are the groups derived from N-(poly)-alkanecarboxylic acids, for example N-(poly)-acetic acids, such as nitrilotriacetic acid, ethylenediamine-tetraacetic acid, diethylenetriamine-pentaacetic acid, N-~-hydroxyethyl-ethylenediamine-triacetic acid, cyclohexane-trans-1,2-diamino-tetraacetic acid, ethylene-diamine-N,N'-di-(o hydroxyphenyl)-acetic acid, N,N'-di-~-hydroxyethyl-ethylenediamine-diacetic acid, bis-(dicarboxy-methyl-aminomethyl) ether or bis-(dicarboxymethyl-aminomethyl) sulphide and especially from iminodiacetic acid.
The chelate-forming ion exchangers can be employed in variously charged ~orms. Depending on the composition of the substrate to be treated, it is advisable to use the exchangers in the H form or in their salt ~orm, pre~erably the form of the potassium9 calcium or magnesium salt.
Furthermore, the use of mixtures of the variously charged forms can under certain circumstances be advantageous. The ion exchangers to be used according to the in~-ention can be used in the form of granules, in bead form or in powder form.
For use in granule form or bead form, chelate-forming ion exchangers with a macroporous matrix are particularly suitable.
The ion exchangers to be used according to the invent-ion are in general employed by adding the chelate-forming ion exchangers to the substrates to be treated by raki~g or digging-over and ensuring that the substrate and the ion exchanger are mixed as intimately as possible with one another.
~e A 15 ~7~ - 4 . , The amount in which the ion exchangers to be used according to the invention are employed per m3 of substrate depends essentially on the heavy metal content of the sub-strate. In general, the resins are employed in an amount such that 0.2-10, preferably 0.5-2, equivalents of chelate-forming group in the ion exchanger are present per 1 equivalent of heavy metal to be fixed. The optimum amount can also be determined, for example, empirically by the so-called cress test. This test is carried out by growing cress on a subst~ate containing heavy metal and determining what amount of chelate-forming ion exchange resin, when added, restores normal growth of the young plants.
The substrates to be treated according to the invention can be either natural substrates such as humus soils, peaty soils, sandy soils, loam soils or clay soils, or syn-thetic substrates) for example substrates based on polyure-thane.
The followin~ Examples i:lustrate the invention.
:~xaTDple s 1,250 g/m3 o~ an ion exchange resin containing imino-diacetic acid groups (in the calcium salt form; matrix: macro-porous polystyrene crosslinked with 8% of divinylbenzene;
iminodiacetic acid group equivalent: 3.8 milliequivalents/g) were worked into five different substrates having a raised content of toxic heavy metalsO Cress was sown after 14 days on the substrates thus obtained and after 12 days the rooting of the young plants was examined; the following results were obtained (t~e rooting was assessed in terms o~ ratings 0 to 6, wherein 0 = no rooting and 6 = normal rooting).
e ~ 15 ~8 - 5 -., , , ~, . .. . ...
106~331 Example No Suh~t~ate ~ IV V
Control _ Cuntreated substrate) 1 1 0 2 0 1 Treated substrate 5.5 5.5 4 5.5 5.5 l~hen the ion exchange resin was employed in the magnesium salt form ~A) or in the form of the calcium-magnesium salt ~B~, instead of in the calcium-salt form, an equivalen~ improvement of the substrate was achieved, as can be seen from the table which follows Example No. Substrate I II III IV V
~ Control 1 1 0 2 0
2 Treated substrate (A~ 5 5 4 6 4.5
3 Treated substrate (B) 5.5 5.5 2 5 4.5 The five different humus substrates ~howed the following heavy metal contents:
Substrate 1: 212 ppm of lead, 70 ppm of copper and 100 ppm of zinc.
Substrate II: 200 ppm of lead, 69 ppm of copper and 76 ppm of zinc.
Substrate III: 148 ppm of lead, 54 ppm of copper and 2070 ppm of zinc.
Substrate IV: 200 ppm of lead, 70 ppm of copper and 74 ppm of zinc.
Substrate V: 216 ppm of lead, 76 ppm of copper and 112 ppm of zinc.
Equally favourable results were obtained when chervil (an~hriscus cerefolium), chicory Cchicorium intybus), tomatoes Clycopersicon esculentum), parsley (petroselinum crispum), leek (allium porrum), salsify (scorzonera hispanica), savoy cabbage Cbrassica oleracea~, onion Callium cepa), radish (raphanus sativus), celery (apium graveolens), carrot (daucus carota), lettuce ~lactuca 1~6'~331 sativa~, spinach (spinacia oleracea), big marigold (tagetes erecta), beans (p~aseolus vulgaris), green peas (pisum sativum) and roses Crosa spec.) ~as used in place of cress (lepidium sativum) for the rooting experiments.
Substrate 1: 212 ppm of lead, 70 ppm of copper and 100 ppm of zinc.
Substrate II: 200 ppm of lead, 69 ppm of copper and 76 ppm of zinc.
Substrate III: 148 ppm of lead, 54 ppm of copper and 2070 ppm of zinc.
Substrate IV: 200 ppm of lead, 70 ppm of copper and 74 ppm of zinc.
Substrate V: 216 ppm of lead, 76 ppm of copper and 112 ppm of zinc.
Equally favourable results were obtained when chervil (an~hriscus cerefolium), chicory Cchicorium intybus), tomatoes Clycopersicon esculentum), parsley (petroselinum crispum), leek (allium porrum), salsify (scorzonera hispanica), savoy cabbage Cbrassica oleracea~, onion Callium cepa), radish (raphanus sativus), celery (apium graveolens), carrot (daucus carota), lettuce ~lactuca 1~6'~331 sativa~, spinach (spinacia oleracea), big marigold (tagetes erecta), beans (p~aseolus vulgaris), green peas (pisum sativum) and roses Crosa spec.) ~as used in place of cress (lepidium sativum) for the rooting experiments.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of treating a substrate capable of supporting the growth of a plant to reduce damage to and/or to reduce heavy metal residues in plants grown on the substrate comprising incorporating from about 0.2 to about 10 equivalent of an insoluble chelate-forming ion-exchange resin into the substrate per equivalent of heavy metal to be fixed.
2. A method according to claim 1, wherein the chelate-forming ion-exchange resin is based on a condensation product of an aliphatic and/or aromatic amine with epichlorohydrin and/or formaldehyde.
3. A method according to claim 1, wherein the chelate-forming ion-exchange resin is based on a macroporous or microporous copolymer of a mono-or polyvinyl compound.
4. A method according to any one of claims 1 to 3, wherein the chelate-forming ion-exchange resin contains an N-(poly)- alkanecarboxylic acid as chelate-forming group.
5. A method according to any one of claims 1 to 3, wherein the chelate-forming ion-exchange resin contains an N-(poly)- acetic acid as chelate-forming group.
6. A method according to any one of claims 1 to 3, wherein the chelate-forming ion-exchange resin contains an imino-diacetic acid group as chelate-forming group.
7. A method according to any one of claims 1 to 3, wherein the chelate-forming ion-exchange resin is employed in the H form or in the potassium calcium or magnesium salt form.
8. A method according to any one of claims 1 to 3, wherein the chelate-forming ion-exchange resin is employed in an amount which provides from 0.5 to 2 equivalents of chelate-forming group per 1 equivalent of heavy metal in the substrate to be fixed.
9. A method according to any one of claims 1 to 3, wherein the sub-strate is a natural soil.
10. A method according to any one of claims 1 to 3, wherein the che-late-forming ion-exchange resin is incorporated into the substrate by digging and/or raking over the substrate.
11. A method of reducing heavy metal residues in a plant grown on a substrate containing a heavy metal comprising growing the plant on a sub-strate treated by a method according to any one of claims 1 to 3.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19742434593 DE2434593B2 (en) | 1974-07-18 | 1974-07-18 | USE OF CHELATING ION EXCHANGE RESINS FOR SUBSTRATE TREATMENT |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1069331A true CA1069331A (en) | 1980-01-08 |
Family
ID=5920916
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA231,624A Expired CA1069331A (en) | 1974-07-18 | 1975-07-16 | Method of treating plant growth substrates |
Country Status (15)
Country | Link |
---|---|
JP (1) | JPS5145055A (en) |
AU (1) | AU497550B2 (en) |
BE (1) | BE831455A (en) |
CA (1) | CA1069331A (en) |
CH (1) | CH609204A5 (en) |
DD (1) | DD126139A5 (en) |
DE (1) | DE2434593B2 (en) |
DK (1) | DK134964C (en) |
ES (1) | ES439539A1 (en) |
FR (1) | FR2278261A1 (en) |
GB (1) | GB1476815A (en) |
IT (1) | IT1040953B (en) |
NL (1) | NL7508582A (en) |
PL (1) | PL98960B1 (en) |
SE (1) | SE7508188L (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USD779674S1 (en) | 2015-02-27 | 2017-02-21 | 3M Innovative Properties Company | Filter element having a connector |
USD786443S1 (en) | 2015-02-27 | 2017-05-09 | 3M Innovative Properties Company | Filter element |
USD792959S1 (en) | 2015-02-27 | 2017-07-25 | 3M Innovative Properties Company | Filter element having a pattern |
US11311752B2 (en) | 2015-02-27 | 2022-04-26 | 3M Innovative Properties Company | Flexible filter element having an end outlet |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9305902D0 (en) * | 1993-03-22 | 1993-05-12 | Bp Chem Int Ltd | Process |
-
1974
- 1974-07-18 DE DE19742434593 patent/DE2434593B2/en active Granted
-
1975
- 1975-07-09 AU AU82889/75A patent/AU497550B2/en not_active Expired
- 1975-07-16 CH CH932775A patent/CH609204A5/en not_active IP Right Cessation
- 1975-07-16 DD DD186819A patent/DD126139A5/xx unknown
- 1975-07-16 JP JP50086249A patent/JPS5145055A/ja active Pending
- 1975-07-16 CA CA231,624A patent/CA1069331A/en not_active Expired
- 1975-07-16 IT IT50542/75A patent/IT1040953B/en active
- 1975-07-17 SE SE7508188A patent/SE7508188L/en unknown
- 1975-07-17 GB GB3005175A patent/GB1476815A/en not_active Expired
- 1975-07-17 NL NL7508582A patent/NL7508582A/en not_active Application Discontinuation
- 1975-07-17 BE BE158373A patent/BE831455A/en not_active IP Right Cessation
- 1975-07-17 ES ES439539A patent/ES439539A1/en not_active Expired
- 1975-07-17 DK DK327075A patent/DK134964C/en active
- 1975-07-17 PL PL1975182121A patent/PL98960B1/en unknown
- 1975-07-18 FR FR7522568A patent/FR2278261A1/en active Granted
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USD779674S1 (en) | 2015-02-27 | 2017-02-21 | 3M Innovative Properties Company | Filter element having a connector |
USD786443S1 (en) | 2015-02-27 | 2017-05-09 | 3M Innovative Properties Company | Filter element |
USD792959S1 (en) | 2015-02-27 | 2017-07-25 | 3M Innovative Properties Company | Filter element having a pattern |
USD886273S1 (en) | 2015-02-27 | 2020-06-02 | 3M Innovative Properties Company | Filter element having a pattern |
US11311752B2 (en) | 2015-02-27 | 2022-04-26 | 3M Innovative Properties Company | Flexible filter element having an end outlet |
US11738218B2 (en) | 2015-02-27 | 2023-08-29 | 3M Innovative Properties Company | Flexible filter element having an end outlet |
Also Published As
Publication number | Publication date |
---|---|
GB1476815A (en) | 1977-06-16 |
FR2278261A1 (en) | 1976-02-13 |
AU8288975A (en) | 1977-01-13 |
PL98960B1 (en) | 1978-06-30 |
DD126139A5 (en) | 1977-06-22 |
NL7508582A (en) | 1976-01-20 |
ES439539A1 (en) | 1977-06-01 |
FR2278261B1 (en) | 1979-05-11 |
JPS5145055A (en) | 1976-04-17 |
BE831455A (en) | 1975-11-17 |
IT1040953B (en) | 1979-12-20 |
DK134964B (en) | 1977-02-21 |
DE2434593A1 (en) | 1976-02-05 |
CH609204A5 (en) | 1979-02-28 |
DK327075A (en) | 1976-01-19 |
DE2434593B2 (en) | 1976-09-02 |
SE7508188L (en) | 1976-01-19 |
AU497550B2 (en) | 1978-12-14 |
DK134964C (en) | 1977-07-25 |
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