the invention relates to the use of organo sulfur containing compounds to stabilize heavy metals ( e . g . cadmium and lead ) found in ash , particularly ash from foundry cupolas , so that the ash will pass tclp testing . organo sulfur containing compounds which will stabilize ash include organo sulfur containing compounds selected from the group consisting of thiocarbamates , thiocarbonates , trimercaptotriazines , alkali or alkaline earth metal salts thereof , and mixtures thereof , preferably dimethyldithiocarbamate , diethyldithiocarbamate , polythiocarbonate , alkali metal salts thereof , trisodium trimercaptotriazine , and mixtures thereof . the amount of the organo sulfur compound used is an amount effective to stabilize any residual metals remaining after treatment with the iron salt , generally this is from 1 weight percent to 12 weight percent based upon the weight of the ash to be treated , preferably from 2 weight percent to 6 weight percent based upon the weight of the ash to be treated . preferably used as the iron salts in the process are ferrous sulfate , ferric sulfate , ferrous chloride , ferric chloride , preferably ferric sulfate . the amounts of iron salt is such that the weight ratio of iron salt to organo sulfur compound is preferably from 5 . 0 : 1 . 0 to 1 . 0 : 5 . 0 , more preferably 3 . 0 : 1 . 0 to 1 . 0 : 3 . 0 . increased amounts of iron salt can be used without detrimental effect on the process , but the costs of the process will be increased . preferably , after the preferred amount of iron salt is added to the mixture , a commodity acid , such as phosphoric acid , hydrochloric acid , or sulfuric acid , preferably phosphoric , will be used to lower the ph to 4 - 5 if the addition of the iron salt has not already done this . preferably the alkaline earth metal containing compound is selected from the group consisting of magnesium oxide , magnesium hydroxide , calcium oxide , calcium hydroxide , and mixtures thereof . most preferably used as the alkaline earth metal containing compound is magnesium hydroxide or magnesium oxide . the weight ratio of alkaline earth metal containing compound to organo sulfur compound is from 1 . 0 : 20 . 0 to 20 . 0 : 1 . 0 , preferably 1 . 0 : 5 . 0 : 5 . 0 : 1 . 0 . the alkaline peat moss extract is a liquid and comprises humic acid , fulvic acid , a blend of humic acid and fulvic acid , and salts thereof . the weight ratio of alkaline peat moss extract to organo sulfur compound is from 1 : 5 to 5 : 1 ., preferably from 1 : 2 to 2 : 1 . the weight ratio of organo sulfur compound to ash to be treated is from 0 . 25 : 1000 to 40 : 1000 , preferably 2 . 5 : 1000 to 20 : 1000 . after the ash is treated by the process , the metal ions are less soluble when exposed to an acidic medium . when the reactants are used under the proper conditions , it is believed that the metal ions become fixed ( a physical binding or immobilization of the metals ) in the aggregate which results after the treated slurry of ash is cured . additionally , stabilization or buffering against the acidic conditions , is accomplished by ph control . this gives additional protection against metals solubilizing under acidic conditions . it should be apparent that the process does not remove the metals from the treated ash . instead it contains the metals in the aggregate which results from treating the ash by the process . a preferred general process for stabilizing the metals in ash is as follows : 1 . add 1000 parts ash ( typically cupola ) consisting of a mixture of bottom ash and fly ash having a weight ratio of 0 : 100 to 70 : 30 , preferably about 50 : 50 , to a batch mixer tank . 2 . add enough water to make an ash / water slurry ( from 5 weight percent to 150 weight percent , preferably 15 to 21 weight percent , of water based upon the weight of the ash ). 3 . add an iron salt ( from 2 weight percent to 6 weight percent , based upon the weight of the ash to be treated ), and if necessary a commodity acid , for instance sulfuric acid , hydrochloric acid , or preferably phosphoric acid , over a period of about 5 minutes to reduce the ph of the slurry to 4 . 0 to 5 . 0 , preferably 4 . 5 to 5 . 0 . 4 . add the organo sulfur containing compound ( amersep mp - 3r ) and alkaline peat moss extract ( oca 15 - 400 ), both in amounts of 0 . 25 % to 10 % based upon the ash to be treated . 5 . add an alkaline earth metal hydroxide over a period of several minutes ( generally 5 minutes to 10 minutes ). sufficient alkaline earth metal containing compound is added to preferably raise the ph to at least 7 . 5 . typically , the organo sulfur containing compound is added first and then the alkaline earth metal hydroxide is added , and mixing is continued for several minutes until the mixture is uniform . 6 . mix the slurry and reagents until they are uniform , typically for approximately 5 to 10 minutes , and allow the treated mixture to cure for about 18 hours or until a hardened aggregate results . after the treatment process , the concentration of unstabilized metals in the cured mixture is measured according to the tclp test to determine if the levels are below the required concentrations . in some applications , it is desirable to add lime to raise the ph of the slurry to facilitate a buffer against the effects of acid rain . sufficient lime is added to the slurry after it is treated with the organic sulfur containing compound and magnesium oxide and / or magnesium hydroxide to raise the ph to about 9 - 11 . the lime is typically added over a period of 5 to 10 minutes until the mixture is uniform . in such cases the slurry is mixed until it is uniform , typically for about 5 to 10 minutes . the epa toxicity characteristic leaching procedure ( tclp ) test is described in test method 1311 , federal register , mar . 29 , 1990 , revised jun . 29 , 1990 , and is herein incorporated by reference . essentially , tclp leach testing involves exposing a sample to an severe acidic conditions which accelerate the leaching process . the leaching process takes approximately 18 to 24 hours for tclp . samples which have concentrations of metals below the concentration levels established by the tclp test are classified as non hazardous . consequently , they can be disposed of less stringently with less expense . as mp - 3r -- amersep ® mp - 3r metals precipitant which is 40 - 55 % by weight sodium dimethyldithiocarbamate in water . as 5320 -- amersep ® 5320 coagulant which is liquid ferric sulfate at a 40 to 50 weight percent concentration in water with about 1 weight percent sulfuric acid . oca 15 - 400 -- oca 15 - 400 , sold by organic products company , inc ., is an alkaline extract of peat moss which comprises a liquid blend of extracts such as humic acid and fulvic acids . the cas # for oca 15 - 400 is 1415 - 93 - 6 . the test procedure used in the following examples is as follows : a one kilogram sample of combined fly ash and bottom ash was treated as follows : 1 . add 300 ml of water to the ash sample , mix one minute . 2 . add 2 % by weight amersep 5320 and mix one minute . 3 . add drew oca 15 - 400 and amersep mp - 3r in amounts as set forth in table i and mix one minute . 4 . add 2 % by weight of mgo and mix seven minutes . table i______________________________________ additive (% by weight ) heavy metals ( ppm ) example oca 15 - 400 mp - 3r cadmium lead______________________________________control 0 0 1 . 46 1 . 031 0 2 0 . 044 0 . 482 1 0 0 . 067 0 . 363 2 0 0 . 064 0 . 334 1 2 0 . 061 0 . 365 2 2 0 . 067 0 . 33______________________________________ the results in table i show that cadmium and lead levels in the extraction of fluid are significantly reduced with the addition of oca 15 - 400 . on the other hand , no synergistic effect is noted when mp - 3r is mixed with oca 15 - 400 .
this invention relates to a process for stabilizing heavy metals in ash . the steps of the process include : preparing an aqueous slurry of ash and water ; decreasing the ph of the aqueous slurry to less than about 5 . 0 in the presence of an iron salt ; treating the aqueous slurry with an organo sulfur containing compound , an alkaline extract of peat moss , and an alkaline earth metal containing compound . heavy metals in ash treated by this process will not leach into the environment .