Paper 

### presented at 

### Symposiumon 

### Cement

### and Concrete 

### in the 

### Global Environment March 10,1993 

### O'Hare Marriott 

### Hotel Chicago, 

### IL



### LEACHABILITY 

### OF SELECTED CHEMICAL ELEMENTS FROM 

### CONCRETE

Howard

### M. Kanare 

### principal Scientist Chemical Services Presbury B. West 

### Senior Scientist Materials Research 

### and Consulting

Construction Technology Laboratories, Inc. 

### 5420 Old 

### Orchard Road 

### Skokie, 

### IL 60077-1030

Phone 708.965.7500

Fax 

### 708.965.6541Kanare, H. M. and West, P. 

### B.*,"Leachability

### of Selected Elements 

### from 

### Concrete," in 

# Proc. Symposium 

### on Cement and Concrete 

### in the Global Environment March 

### 1993,PCA.

SUMMARY Eight portland cement concretes were made 

### from fourcements and 

### two aggregates, one siliceous and one calcareous. A concrete cylinder 

### from each was

### crushed according toU. S. Environmental Protection Agency 

### SW-846 protocol and tested by the Toxicity Characteristic Leaching Procedure. In addition to eight elements

### specified in the Resource Conservation and Recovery Act 

### -arsenic (As), barium @a), cadmium (Cd), chromium 

### (Cr), lead (Pb), mercury (Hg), selenium(Se), and silver (Ag)

### - the concentrations of

### four other metals were also determined: antimony (Sb), beryllium (Be), nickel (Ni), and thallium (Tl). Analysis for most metals was performed by graphite furnace atomic absorption spectrophotometry to obtain the lowest possible detection limits consistent with sample compositions and analyte concentrations. Results indicate metal concentrations in leachate 

### are 

### all less than one-tenth RCRA regulatory limits, and many concentrations are below detection limits. Chromium TCLP cement values correlate with concrete leachate values while lead values do not.
A second series of leaching tests was performed with deionized water in place of acetic acid solution. These tests are called "water leaching by TCLP protocol" 

### in this paper. Four of the concretes representing both aggregates and two of the cements were tested by this procedure. Analysis of the concrete extracts was performed for the same twelve metal analytes. Concentrations of metals in water leachate 

### are generally similar to 

### r lower than concentrations in acid leachate.
A third series of tests was performed on 

### all eight concretes generally following ANSYNSF 61 to simulate leaching with drinking-quality water as would 

### ccu in a municipal water supply system. Concentrationsof As, Ba, Se, and Ag were nearly 

### all below detection limits and well below NSF specification 

### maxima. Concentrations of Cr, fluoride, and nitrate were all belowNSF specification maxima. Despite precautions to work with high-puxity reagents and ultra-clean vessels, control samples showed Hg and Pb levels indicating probable contamination from the vessels 

### used for soaking the concrete cylinders. 

### This work points out how difficult it is to perform these tests when reporting limits are required in the sub-partsper-billion range.



### * principal Scientist and Senior Scientist, respectively, Construction Technology Laboratories, Inc., Skokie, 

### IL 60077.

1BACKGROUND This report examines 

### two issues concerning the leachability 

### of 

### tracemetals from concrete: leachability of crushed 

### concxete specimens

### withdilute acetic acid and 

### water following the 

### U. S. 

### EPA Toxicity Characteristic Leaching Procedure, and leachability 

### from whole concrete specimens with synthetic drinking water following 

### ANSVNSF 61

### procedures. The 

### purpose of 

### this work is 

### todetermine if selected metallic elements 

### are leached 

### in significant quantities and to 

### begin 

### to understand the differences in 

### results from leaching 

### tests 

### run on the same concretes according 

### to different protocols. Issues include 1)whether leach tests on concrete batch components 

### are additive and whether such tests can 

### be 

### used 

### to predict the leachate composition 

### of the hardened concrete; and 2) how does particle 

### size affect leachate concentration.

EXPERIMENTAL Cement Four cements were chosen from among the nearly 100 cements submitted for analysis and reported in the Portland Cement Association publication 

### An Analysis of

### Selected Truce Metals in Cement and KilnDust (PCA Publication SPllO). These cements were chosen to represent a range of leachable metal concentrations, various cement manufacturing process types, and fuels used. Cements from participants 27,61,82,and 84 were selected and the 

### data for total metals and TQ,P metals were obtained hm that report. Table 1 indicates the types of cements, manufacturing processes, raw materials, and fuels used to make these four cements. Tables 2 and 

### 3 show the physical and chemical properties 

### of the cements. Cement from participant

### 82 is an 

### ASTM 

### C 150Type 

### IA (air entraining) cement and the other 

### three cements are either Type I 

### or Type 

## II. Cements 82 and 84 were made using supplemental waste fuels.
Total and TCLP trace metal concentrations for the cements 

### are hown in Tables 4 and 5. Figure 1 shows the concentrations of barium, chromium, and lead 

### in acetic acid TCLP leachate from the four cements in comparison to the range and mean concentrations in 

### all cements from the PCA study of U. 

### S. and Canadian cements. Aggregates A mixed carbonats-siliceous sand from Elgin, Illinois was used for all eight concrete batches. Two kindsof coarse aggregate were selected 

### from among materials fiequently used at 

### CTL: siliceous coarse aggregate from Eau Claire, Wisconsin (a 60/40 ratio 

### of two 

### size fractions 

## - 19mm to 13mm and 10

### mm to 5 mm [3/4-in to 1D-inand 3/8-in to 3/16-in] and dolomitic coarse aggregate from Thornton, Illinois 

### 19 mm topsize 

### [3/4-inJ). The coarse and fine aggregates have well-known service histories and have been used for 

### many years in research projects sponsored by the Portland Cement Association. TCLP tests were carried 

### out on the sand and each aggregate fraction. The results of these TUP tests 

### are shown Table 

### 6.

2

### Concrete Mixes Concrete mixes were designed to 

### obtain roughly 

### 30 Mpa (4500 psi) compressive strength 

### with a water-cement

### ratio of 0.55. Coarse aggregate:sand 

### ratiowas 

### 6040 and the cement content was 

### 335 kg/m3 (564 lb/cu yd) for all concretes. Municipal (Skokie, Illinois) tap water was used without additional processing. Water content was kept constant in order to keep the weight percent cement in the concretes the same while the slump was allowed 

### to vary. Concrete mix designs are shown in Table 7. Concretes made

### with Eau Claire aggregate were designated EC27, EC61, EC82, and 

### EC84 and those with 

### Thornton dolomite were designated TD27, TD61, TD82, and 

### TD84 where the numbers indicated the participant number of the cements. For each batch of concrete, 0.02 m3 (3/4 cu 

### ft)of concrete was mixed in a pan mixer, the air-content was obtained, and eight 75 x 150mm (3 x 6 

### in) cylinders were cast in polypropylene cylinder molds (DesLauriers, Bellwood, 

### IL)without release agent. Cylinders were consolidated by rodding except TD27 which 

### required vibration. Three cylindersof each mix were tested at 28 days for compressive strength. Slump, air content, unit weight, and 28-day compressive strengths shown in Table 8. Concrete cylinders were cured at 23' 

### C (73"

### F)in the polypropylene cylinder molds with low-density polyethylene snap-fit covers. Samples for TCLP (acid and water) were demolded at 60-70 days of age, immediately prior to crushing for the extraction tests. Samples for the ANSYNSF61 drinking water tests were used at 16months 

### of age.

LEACHING PROCEDURES Sample Processing Each cylinder was demolded and broken into chunks with a steel hammer. These chunks were passed through a jaw crusher (BICO-Braun, Burbank, California) with hardened steel jaws set to produce particles mostly less than 9.5 mm (3/8 in). The crushed samples were passed through a brass 9.5 mm sieve. The question is often asked whether crushing and grinding contaminates samples with metals from the processing equipment such as jaw crushers, disc pulverizers, 

### or swing mills. Data from a project using clinker give some insight into possible contamination in the processing. A sample of a relatively dense portland cement clinker was passed three times through the steel-plate jaw crusher (BICO-Braun, Burbank, CA) then ground with a ceramic mortar and pestle to pass a 150pm (No. 100 U. S. Standard) sieve. A control sampleof clinker was processed by grinding with a ceramic 

### mortar and pestle to the same fineness. Flame AAS analysis for nitric acid-soluble nickel and chromium indicated small increases due t6 thejaw crusher processing (71.9vs. 75.8 mag 

### Cr and 15.1 vs 16.1 mg/kg Ni). For comparison, chrome alloy disk pulverizer plates (Model UA-2000, BICO-Braun, Burbank, CA) substantially increased chromium and nickel concentrations (71.9 vs. 166.3 mag 

### Cr and 15.1 vs 22.2 mag Ni). Milling 30 sec in a tungsten carbide swing mill 

## (W. Bleuler, Zollikon; container Cat. no. 8504 from Spex Industries, Edison, New Jersey) did not contribute significant iron, nickel, or chromium, although cobalt increased (6.6 vs. 11.3

3mg/kg). We

### m not aware 

### of a practical 

### processing method that 

### would eliminate 

### all metal contact 

### andpermit reduction 

### of concrete 

### cylinders 

### to 9.5 mm 

### (3R-h)

### size.
TCLP (Acetlc Acid) EPA Method 

### 1311 was followed. For each

### crushed conmte sample, 

### 100 g was weighed into a 

### 2

### L polypropylene smw-cap

### jar and 

### 2000 g 

### dilute acetic acid 

### @H 2.88k0.05) was 

### added. The 

### jars were capped and tumbled in a four-bottle 

### rotary agitation apparatus (Analytical Testing and Consulting Services Model DC-20, Warrington, Pennsylvania) at 

### 30 rpm for 

### 18 

### hr at 

### 23' C 

### (73' 

## F). Leachate was suction filtered thorough glass-fiber fdters (Whatman 

### GF/F) and transferred 

### topolyethylene bottles. The pH 

### of each solution was 

### recorded. The filtered leachates we= acidified 

### to pH 

### 4 with nitricacid
TCLP (Water) The procedure presented above was followed using ASTM D 

### 1193 Type I water instead of 

### dilute acetic acid. Analysis Samples were digested and analyzed according to EPA 

### SW-846 methods by atomic absorption spectrophotometry. The methods followed procedures described in the PCA cement and 

### kiln dust report

### (SP110). RESULTS 

### OF TCLP TESTS
Estimates of Potential Metal Concentrations in Leachate Two estimates 

### ofpotential metals concentrations 

### in leachate were obtained by using the cementTUP result in one case (called the minimum estimate) and using the cement total metals result in the other case (called the maximum estimate). These results were combined with TUP results from the aggregates. If the TCLP results are additive, their sum should be a reasonable estimate 

### of concentrations in the concrete leachate. The minimum estimate was obtained after first calculating for each metal the contribution from the cement 

### o the potential leachate concentration using the weight fraction 

### of cement in the concrete

### (0.1397) 'times the cement 

### TCLP value for each analyte. 

### This value was then added to the weighted sum of contributions from sand 

### (31.19% 

### of FA 

### TUP)and from coarse aggregate

### (47.15% of CA 

### TCLP)to give the minimum estimate. This value may be similar to actual leaching 

### data if TCLP results 

### are additive. As an example here is the calculation 

### of the minimum estimate for barium 

### in the 

### TCLP extract 

### of concrete 

### TD61: (0.1397x 

### 0.93)+(0.3119 x 

### 0.33)+(0.4715 X 

### 0.16) = 

### 0.130+0.103+0.075 = 

### 0.31 mg/L The maximum estimate was obtained after firstcalculating for each metal the maximum contribution from the cement to the potential leachate concentration using the weight fraction 

### of cement 

### in the concrete

### (0.1397) times thetotal metal in cement. 

### This value was thenadded to the weighted sum of the contributions from sand 

### (31.19% of FA TCLP) and from coarse aggregate 

### (47.15% of CA TCLP) to give the maximum estimate. 

### This value would occur if 

### all of the metal analyte contained in the cement contributed to the concrete TUP 

### result. As



### 4an example here is the calculation 

### of the 

### maximum estimate 

### far barium 

### in the TUPextract 

### of concrete TD61: (0.1397 x 8.15)+(0.3119 x 0.33)+(0.4715 x 0.16) = 0.139+0.103+0.075 = 1.32 mg/L
Leachlng Results The TCLP (acid) concrete data 

### are shown 

### in Table 9. The concentrations of 12 metals were determined in leachates from 

### 8 concretes producing 96 individual measurements; fifty of those results

### are below detection limits. For the individual metals analyses 

### of the concrete TCLP (acetic acid) extract, all results for arsenic, beryllium, and selenium are below detection limits and 

### six of the eight concrete leachates for antimony, cadmium, and thallium are below detection limits. For the remaining six metals, the leachate concentrations 

### are below detection limits for two of eight results for mercury and nickel ;one of eight results is below detection limits for each of the rest of the metals. Normalized concentrations 

### of these six metals in the eight concrete 

### TCLP extracts 

### are presented in Figwe 2. The eight results that fall below detection limits

### are shown at the detection limits. Concentrations 

### are normalized to the individual RCRA limit for each metal and plotted on a logarithmic scale. The plot indicates all results 

### are less than Moth the RCRA limits. Chromium and silver normalized concentrations (with one exception ) 

### are between l/lOth and 1/1OOth of their 

### RCRA limits. Most of the normalized concentrations for barium, lead, mercury, and nickel fall between 1/100th and 

### 1/1OOOth of their respective RCRA limits. Comparison of TCLP (acid) and TCLP (water) The TCLP water data are shown in Table 10 and a comparison of selected acid versus water results is shown in Table 11. In most instances the TCLP acid leaching result falls between the maximum and minimum estimate while the TCLP water leaching result falls near or below the minimum estimate. (See Figure 2a.) Relation Between Cement and Concrete Approximately 15% of the crushed concrete is not recovered after filtering and drying the TCLP (acid) residue. This corresponds to the amount of cement in the concrete batches. The recovered solids consist of aggregate with little or no cement paste adhering. Whether the metals remain in solution or precipitate and become trapped in the filterresidue determines the measured concentrations.
Much interest surrounds chromium and lead levels in leachates. Figure 

### 3 indicates thatTUP chromium from the cements is correlated (R4.92)with TCLP (acid) chromium from the concretes. Total chromium in the cements also correlates (R4.89) with TCLP (acid) chromium from the concretes (Figure 4). While leachable chromium from all eight concretes is less than one-tenth of the 5 mg/L RCRA limit, these correlations may be useful 

### to cement producers monitoring potential leachable chromium.
No relationship appears to exist between lead levels in cement and TCLP conmete values (Figures 5 and 6).

5DRtNKlNG WATER LEACHING Eight 

### 3 x 6

### in concrete test 

### cylinders were 

### tested generally following 

### procedms in 

### ANSI/NSF 61-1991, 'DrinkingWater System

### Components-Health Effects," 

### The purpose of these 

### tests is to 

### simulate exposm of drinkingwater 

### to the 

### interior surface 

### of concmte pipe 

### as the water 

### is transportedin a municipal water distribution 

### system. These 

### tests consist of conditioning the specimen followed by exposure to simulated drinking water containing buffering, hardness, and chlorinating agents. Experimental A dedicated

### room maintained at 23-24' C (74-76" 

### F) was prepared by draping 0.15-mm (6-mil) polyethylene sheets to enclose a space roughly 2.5 x 

### 3 x 2.5 

### m (8 x 

### 10x 8 Et) to 

### minimize airborne contamination. Tacky mats (Liberty Industries) were placed immediately inside and outside the door of the 

### mom to trap particulates on workers feet. 

### To assure sufficient supply 

### of high-purity water, a water-polishing station (Barnstead Nanopure, dual Ultrapure cartridges) fed from service &ionizer cartridges was placed in the room. Each concrete cylinder was brushedwith a steel-bristle brush under cold tap water and rinsed with 

### ASTM D 1193 Type 

### II deionized water. Cylin&rs were handled throughout with latex surgical gloves. Each cylinder was placed in a 19 L (5-gal) FDA approved, white polyethylene bucket (Philips Container Co.)which had been previously washed with soap, rinsed with tap water, washed with acid, washed with base, rinsedwith tap water, and rinsed with Type

### II water. Stock solutions of sodium bicarbonate 

### (0.04 

### M), calcium chloride 

### (0.04 

### M), and sodium hypochlorite (1.5 

### ma residual total chlorine) were prepared using ACS reagent grade chemicals and

### Type I water. Conditioning water at pH 8 was made from the stock solutions using 260 mL 0.04 M NaHCO3,26O mL

### 0.04 

### M CaC12,13.9 mLNaOC1, and Type I water 

### to make 10.4 L. 

### This volume gave a surface 

### area to volume ratio of 43.7 cm2/L based on a 910-mm (34) diameter pipe. Specimens were fistexposed

### to conditioning water/disinfecting solution containing 50 mg/L available chlorine. Subsequent exposures contained 

### 2 m& available chlorine. Specimens were immersed 

### in the conditioning water for 12 days with a change of water every 

### 24 hours, and 

### for two additional days with no change of water. The conditioning water was decanted and specimens were immersed in pH 8 extraction water 

### of the same concentration as the conditioning water, at 23-24" C (74-76" 

### F) for 16

### hr 

# . Extract water samples were decanted into pre-cleaned 125 mL (4 oz) amber glass bdttles far mercury analysis and into 2 L 

### (64 oz) polyethylene bottles for other analytes. Nitric acid (11mL, Baker Instra-Analyzed, 70%)was added to stabilize the solutions for metals analysis atpH 4. Five mLpotassium dichromate/nihic acid solution (25 mL70%HNO3 plus 0.068 g K2Cr2O7, diluted to 500 mL)was addedto stabilize the solutions 

### for mercury analysis. Samples were maintained at room temperatm until analysis. A separate sample of each extraction water was taken for nitrate analysis to which no stabilizing agent was added.

6At 

### CX'L,samples were analyzed by graphite 

### furnace atomic absorption spectrophotometry according to EPA SW-846 methodsfor As, 

### Ba,Cd, Cr,Pb, Se, and Ag. Mercury was analyzed by cold vapor AAS. 

### Fluoride was determined 

### by double 

### standard additions using a selective ion electrode. Nitrate wasdetermined using a colorimetric test kit (Hach 

### NI-10). Sample volumes and instrumental settings were chosen

### to give reponing 

### limits generally onetwentieth 

### or less of the Drinking Water Standards. Split samples also were analyzed according 

### to EPA SW-846 methodsat TEI Analytical, Niles, Illinois, using GFAAS for As, 

### Pb, and Se; inductively coupled plasma spectrometry for Ag, Ba, and Cd; and Hg by cold vapor

### AAS. Fluoride was determined by ion chromatography according to ASTM D 4327. Reporting limitsat TEI were generally equal to or better than one-tenth of the Drinking Water Standards.

Results and Discussion To be listed as acceptable under the ANSI/NSF 61 protocol, drinking water system components must produce leachates with analyte concentrations less than one tenth theU. 

### S. EPA National

### Primary Drinking Water Standards. Results of analyses fromCTL and 

### TEI laboratories are shown in Table 12. For comparison, the relevant drinking water 

### standards are shown following the laboratory results. (For a complete set of drinking water standards, contact the EPA Safe Drinking Water Hotline at 800-426-4791 Monday-Friday 8:30am

### 5 pm EST). Values for As, Cd, Se, and Ag are nearly

### all below reporting limits. Concrete extracts contained Ba and Cr at lessthan one-tenth the drinking water standards. One approach for comparing TCLP and ANSWSF 61 protocols is to normalize results based on surface area to volume (SAV) ratios. Sieve analysisof a 

### TCLP (water) residue was used to calculate the surface area of the residual concrete particles, yielding a surface area of 3440 cm2/100 g. (This calculation

### assumed spherical particles. Since most surface area is in the finest fraction, which contains nearly equant particles, this assumption is reasonable. However, surface roughness, cracks, and permeability were ignored. Thus, the calculated surface area is likely lower than the actual surface area) In 2 L of 

### TCLP leachate this is an SAV ratio of 1720 cm2L. The ANSYNSF 61 tests used an SAV of 

### 43.7 cm2L. The ratio of SAV- to SAVNsF is approximately 40:l. Dividing Cr TCLP (water) values by 40 yields results approximately eight times higher than the drinking water results, suggesting that permeability of the relatively small crushed concrete particles is responsible for some Cr leaching. Lead and mercury in one control sample were higher than in any of the leachates, suggesting contamination of at least one control solution. Mercury levels were 10-20 times higher than expected in tap water and drinking water controls. To investigate the source of lead and mercury in control samples, duplicate samples of water were collected in glass bottles containing the nitric acid-dichromate preservative described above, at 

### the final water deionizer just before filling the polyethylene buckets. Additional samples were taken from a second

7deionizer usedin a different

### part 

### of 

### C2L"s chbistry 

### laboratory. The samples 

### were 

### testedfor 

### mercury and lead by AAS, yielding the 

### following xesults: Concentration, pg/L 

### @pb) 

### Hg Pb 

# Lab:m 

# rn mrn deionizer 1* 

### 0.06 n/a q0.2 

### n/a deioniZer2* 

### 0.03 n/a 

### <0.3 n/a control 

### I? 0.9 

### 3.2 5.8 

### 3 control 2? 0.5 

### 0.3 1.0 

### 3 tap water? 0.2 

### 0.7 2.7 n/a *Mean of duplicate determinations. n/a=notanalyzed materanalyzed after soaking in polyethylenebuckets, with no concrete,for la1 hr. We believe that contamination from the polyethylene buckets 

### (or less likely, airborne sources) caused the concentrations of 

### mercury and lead in controls to exceed levels in the concrete leachates. According

### to State of Illinois reports, the municipal water supply used to make concrete should have contained less than 

### 0.05 clg/L (ppb) Hg. This water passed through service deionizers, plastic hoses, and the final pflcation deionizer before going into the buckets. A water purity meter at the final deionizer indicated resistivity greater than 18 MSZ-cm at all times. These observations indicate the difficulty 

### of performing analyses at such low levels. The use of glass containers, properly prepared, should be preferred over plastic. Some 

### virgin plastic vessels might be suitable if they do not contain any inorganic pigments, fillers, or anti-oxidants.
Rather than normalize results for lab-versus-field surface area-to-volume ratios,we performed the tests at the SAVfratio 

### for a 910-mm (34)diameter pipe and with soaking time precisely 16k1 

## hr. This approach was taken since concretes generally have low, but finite permeability. While leachate from steel pipe probably can be considered 

### to come 

### from the surface

### or an extremely 

### small depth, the whole volume of a concrete specimen should be considered 

### as potential source 

### of leachable substances. Since the kinetics of heavy metal leaching are not precisely known and depend on individual concrete specimen permeability, we felt it would 

### be useful 

### to obtain results without "over-concentration'' 

### of leachate 

### followed by normalization,if instrument detection limits were acceptable. It 

### will be useful to have 

### data on the changing rate of leachability 

### of 

### trace metals 

### as 

### a function 

### of conditioning time. Due to the apparent contamination by lead and mercury in at least some samples, it would be prudent 

### to repeat the analyses for these metals. Othenvise, it appears that metals, 

### fluoride, and nitrate concentrations for the 

### two aggregates and four cements tested do not present concems in drinking water leachates from concrete.

8ACKNOWLEDGEMENTS
This investigation was sponsored by 

### the Portland Cement Association under Research Projects 90-7 and 90-7a. Financial 

### support 

### fromPCA 

### is gratefully acknowledged. The opinions and findings expressed in 

### this report (PCA R & D Serial 

### No. 1925) are those of the authors and not necessarily those 

### of the Portland Cement Association.The authors also wish to acknowledge CTL staff who contributedto 

### this work including Willy Dziedzic (concrete mix designs and supervisionof batching), JoAnne Delles (analytical laboratory supervisor), and Sebastian Padiyara 

### (primary analyst).

9Table 1. CEMENTS USED FOR CONCRETE LEACHING STUDY

Cement No.: No. 27 No. 61 No. 82 No. 84 Cement Type: Type I Type I Type IA Type 11 Process Type: Preheater and Wet precalciner with bypass
Raw Materials: Limestone Clay Sand Iron Oxide

Fuels: Coal Petroleum Coke Preheater

Limestone Limestone Shale CI ay Sand 

### Mill Scale Iron Dust
Natural Gas Limestone Clay Silica Iron

Coal Petroleum Coke Hazardous Waste Waste Solvnts Whole TiresTable 2. ASTM CEMENT AND MORTAR TESTS

Blaine (ASTM C 204) Surface Area, cm2/g L.O.I. (ASTM C 114), 

### Yo Insoluble Residue (ASTM C 114), % Mortar 3d, MPa (psi) Strengths (ASTM C 109) 7d, MPa (psi) 28d, MPa (psi) Initial Vicat (ASTM C 191), hours Autoclave Expansion (ASTM C 151),% Air Content of Mortar (ASTM C 185), % Cement 27 Cement 61 Cement 82

3380 3640 4380 1.56 1.48 3.01 0.28 N.D. 0.61 22.0 (31 90) 21 

### .O (3050) 18.1 (2630) 30.7 (4450) 29.6 (4300) 22.1 (3200) 43.0 (6230) 39.8 (5770) 27.1 (3930) 1 :25 1 :57 2:53 0.05 co.01 0.1 2 9.4 8.8 18.9 Cement 84

4120 1.31 0.49 27.2 (3950) 32.9 (4770) 40.4 (5860) 1 :48 0.03 7.8

Note: N.D. value not determined.TABLE 3. CHEMICAL ANALYSIS OF CEMENTS, wt % 

# u MAl 

# u NQLU 20.85 21.1 1 

### 20.33 20.59 4.55 4.56 4.08 4.53 2.34 2.43 3.39 2.96 63.88 64.05 60.47 63.69 2.45 2.1 1 4.36 2.71 3.34 2.85 3.00 2.74 0.00 

### 0.08 0.1 8 0.08 0.51 0.62 0.79 0.52 0.1 6 0.23 0.25 0.21 0.02 0.1 9 0.1

### 0 0.06 0.04 0.1 2 0.08 0.05 0.04 0.03 0.07 0.1

### 5 

## L5§ 148 

# u La 99.75 99.86 100.1 1 99.62

57 

### 17

9 

### 7 55 19

9 

### 7 49 22

6 10 

### 58 15

8 9

## Analvta Antimony Arsenic Barium Beryllium Cadmium Chromium Lead Mercury Nickel Selenium SiIver Thallium

Analyte Antimony Arsenic Barium Beryllium Cadmium Chromium Lead Mercury Nickel Selenium SiIver Thallium TABLE 4. TOTAL TRACE METALS IN CEMENTS, 

### mg/kg



## <o. 19 92.9

1 

## .lo ~0.05 

### 33.8

8.11 

### c0.062 23 c3 c0.4 46

7.62 <0.19 19.0 163 1.65 ~0.05 99.3

4.62 c0.004 <12

c6 10.3 <0.2 co.19 9.09 1.32 0.04 65.0

5.95 <0.01 21 c4 

### 275

7.06 0.20 

## <o. 1 9 70.6 197 1.51 

## <o. 1 

### 3

6.45 0.0255 167

76 <4 ~0.6

8.03

TABLE 5. TCLP TRACE METALS IN CEMENTS, mg/L No. 27 No. 

### 61 

# u NQa3

<0.0163 co.010

0.71 co.ooo1 <0.0010

0.371 c0.005 c0.0006 co.

### 1 

### 9 c0.006

0.055 c0.03 c0.02 

### <0.035

0.93 c0.0002

0.00107 1.05 0.01

## a <0.00012 c0.03 

### <O.005

0.068 ~0.004 <0.02 <0.060

1.58 0.00008 0.001 85 

### 0.713 0.0080 co.ooo1 c0.05 c0.02

0.071 c0.008 0.0040 co.019

1.59 0.00059 co.oooo9

1.22 0.0049 0.00023 <0.08 ~0.004

0.056 -c0.007

### TABLE 6. 

### TCLP 

### (acid) EXTRACTS FROM 

### AGGREGATES, 

### mg/L 

## Analvte Elain Sand Eau Claire 

### 3/4" Eau Claire 

### 3/8" Jhornton Antimony Arsenic Barium Beryllium Cadmium Chromium Lead Mercury Nickel Selenium 

### Si Iver Thallium 

### c0.0022 <0.003

0.33 ~0.00062

0.00068 c0.04

0.007 <0.00007 <0.08

0.011 

### 0.0522 0.006 <0.0022 ~0.003

0.33 

### 0.00067 0.00046 ~0.04

0.009 <0.0003 c0.08 <0.006 <0.01 

### <0.002 

### <0.0022 ~0.003 ~0.33

0.00047 <0.00021 ~0.04 e0.007 CO.08 

### c0.006 <0.01 

### C0.002

0.00008 

### ~0.0023 c0.014

0.1 6 <0.00015 

### <0.00017 c0.07

0.018 

### 0.00039 0.18 <0.010

0.0422 e0.002

### TABLE 7. CONCRETE 

### MIX DESIGNS, 

### kg/m3 

### (pcy)

Cement Water Elgin Sand Coarse Aggregate 

### 19-1 3 mm 

### (3/4-1/2 in) 

### 10-5 mm 

### (3/&3/16 in) 

### 19 mm 

### (3/4 in) topsize Siliceous 

### Eau Claire



### 335 (564) 184 (310) 775 (1 

### 307) Calcareous Thornton Dolomite


### 335 (564) 184 (310) 747 (1 259)

695 (1 

### 172) 463 (781 ) 

### 1129 (1903)

W/C = 

### 0.55 Coarse Aggregate to Sand Ratio = 

### 60:40TABLE 8. PROPERTIES OF CONCRETES
Eau Claire Siliceous Coarse Aggregate
Strength 

### @ 28 days, MPa(psi) Slump, mm (in.) 

### Air Content, % Unit Weight, kg/m3 (pcf)

Thornton Dolomite

### Coarse Aggregate
Strength 

### @ 28 days, MPa (psi) 

### Slump, mm (in3 Air Content, % Unit Weight, kg/m3(pcf) EC-27 44.1 (6390)

120 (4.7) 1

## .o 2409 (1 50.4)

TD-27 33.2 (481 0) 25 (1.O) 1.3 2384 (148.8) EC-6 1 38.1 (5520)

115 (4.5)
t .9 2384 (148.8)

TD-61 41.4 (601 0)


### 90 

### (3.5) 1.6 2377 (148.4) 

## Ec-82 27.2 (3950)

200 (7.8)

6.2
2291 (1 43.0)

TD-82

19.0 (2750)

180 (7.2) 6.5 2246 (140.2) 

## EC-84 33.0 (4790)

195 (7.6) 0.6
2425 (151.4)



## TD-84

38.1 (5520)

160 

### (6.3)

1.2 2387 (1 49.0)TABLE 9. TCLP 

### (acid) EXTRACTS FROM CONCRETES, mg/L 

## Analvte Antimony Arsenic Barium Beryllium Cadmium Chromium Lead Mercury Nickel Selenium Silver Thallium

Analyte Antimony Arsenic Bariu m Beryllium Cadmium Chromium Lead Mercury Nickel Selenium Silver Thallium 

## EC27
C0.0022 <0.008

0.44 <0.00004 c0.00023 ~0.04 <0.012
<O.08 c0.006 <0.002

0.000346

0.0655

TD27


### ~0.0023 e0.005 

### <O.07 <0.00022 <0.00017

0.08 0.023 <0.00006

0.29 <0.011

0.0766 0.007 

## EC61
~0.0025 <0.008

0.68 <0.00022



### 0.00153 0.19 0.01

### 7 0.000082 co. 

### 1 

### 4 <0.009

0.11 

### c0.002

TD61



### ~0.0023 co.019

0.53 <0.00022 <0.00017

0.21 0.019 <0.00003

0.1

### 4 ~0.005

0.0821 <0.002 

## EC82
c0.0025 

### ~0.005

0.9 <0.00022 <0.00017

0.1 9 0.025 0.000406 0.17 <0.009

0.0766 c0.002



## TD82
~0.0023 c0.007



### 1.05 <0.00022

0.00543 0.1 2 0.016 0.000344 

### 0.21 <0.023

0.071 c0.002 

### EC84
0.0204 <0.019

0.69 <0.00022 c0.00017

0.3 0.013 0.000416 0.29 

### e0.007

0.0788 0.006



## TD84 0.01 96 C0.013

0.71 <0.00022 <0.00017

0.22 0.02 0.00032 

### 0.3 <0.005 <0.01 <0.002TABLE 10. TCLP 

### (water) EXTRACTS FROM CONCRETES, 

### mg/L 

## Analvte 

## EC82 EC84 

## TD82 TD84 Antimony Arsenic Barium Beryllium Cadmium Chromium Lead Mercury Nickel Selenium Silver Thallium 

### e0.016 <0.0035

0.37 <0.0007 <0.0013

0.0597 <0.022 <0.000007 ~0.007 <0.01 e0.086 <0.002 <0.016 <0.0035 <0.2 <0.0007 <0.0013

0.208 <0.022

0.000433 

### <0.007 <0.014 

### ~0.086 co.001 <0.0092 <0.0035

0.29 <0.0002 <0.0011 c0.085 e0.016

0.00078 0.0285 e0.008 ~0.086 <O .004 

### <0.0092 <0.022 g0.3 

### <0.0002 <0.0011 

## <o. 1 

### 1 <0.016

0.000339 0.0435 

### <0.008 

### <0.086 <0.002Table 11. Summary 

### of Differences TCLP Extracts 

### of Concretes Water 

### vs. Acetic Acid

(concentrations in mg/L in leachate) Acetic Acid Water SAMPLE TD82 Barium 1.05 Cadmium 

### 0.00543 Chromium 0.1 

### 2 Nickel 0.21

SAMPLE EC82 Barium 

### 0.9 Chromium 0.19 Nickel 0.1 7

SAMPLE TD84 Antimony 0.01 

### 96 Barium 0.71 Chromium 0.22 Nickel 

### 0.3

SAMPLE EC84 Barium Chromium Nickel Thallium 

### 0.69 

### 0.3 0.29 

### 0.006 

### 0.29 <0.0011 

### <0.085 

### 0.0285

0.37 0.0597 <0.007



### ~0.0092

c0.3 c0.11 

### 0.0435

c0.2 0.208 c0.007 co.001TABLE 12 MEASURED CONCENTRATIONS IN DRINKING WATER LEACHATES. 

### aJimQkm control 

### 1 control 2 tap water 

### EC27 TD27 EC61 TD61 EC82 TD82 EC84 TD84

control 

### 1 control 

### 2 tap water 

### EC27 TD27 EC61 

### TD61 EC82 TD82 EC84 TD84

control 

### 1 control 

### 2 tap water 

### EC27 TD27 EC61 TD61 EC82 TD82 EC84 TD84 

### Menic (urn 

### CTL TEI 6.8 4 

### 6.8 <5 

### 4.8 da 

### 6.8 <5 

### 4.8 <5 

### 4.8 <5 

### 4.8 <5 

### 4.8 <5 

### ~2.8 <5 

### 42.8 <5 

### 42.8 <5 Chromium (u&) 

### CTL 

### TEI

0.2 <9 <0.2 <9

0.7 n/a 

### 0.2 <9 <0.2 <9 0.2 <9 0.3 <9 <0.2 <9 0.2 <9 

### 0.3 <9 0.3 

### <9 Selenium CQ@J 

### CTL TEI 

### ~0.3 <1 

### ~0.3 <1 

### <0.3 n/a 

### ~0.3 

### <1 

### <0.3 <1 

### ~0.3 <1 

### ~0.3 <1 

### ~0.3 <1 

### <0.3 <1 

### ~0.3 <1 

### ~0.3 <1 

### Barium CTL 

### TEI <1

### .7 

### 60 4.7 QO 

### 18 

### da 4.7 QO 

### g1.7 

### 60 4.7 QO



### 2 40 

### 4.7 40



### 4.2 40 <1 

### .7 40 4.7 

### QO
Lead (ut&)* CTL TEI



### 5.8 3 

### 1

## .o 3 

### 2.7 n/a 

### 1.1 

### 2 2.1 3 

### 1.4 2 0.9 

### 2 0.9 3 

### 1.2 2 0.9 

### 3 1.1 

### 4

Silver (urn CTL TEI ~0.4 

### <8 <0.4 <8 

### c0.4 n/a 

### <0.4 

### <8 <0.4 

### <8 ~0.4 

## <a ~0.4 

### <8 ~0.4 e8 

### <0.4 <8 

### ~0.4 <8 

### ~0.4 <8 

### Cadmium (UelL) 

### CTL TEI c0.02 <0.02



### 0.08 c0.02 

### <0.02 <0.02 <0.02 c0.02 <0.02 g0.02 c0.02 4.6 4.6 

### n/a



### 0.8 4.6 4.6

3.7 

### 4.6 ~0.6 

### <0.6 <0.6

Fluoride (m CTL 

### TEI 

### 0.02 4.03 0.02 <0.03 0.5 n/a 

### 0.01 4.03 0.02 <0.03 0.01 ~0.03 0.01 ~0.03 0.02 ~0.03 0.02 <0.03 

### 0.02 ~0.03 0.01 ~0.03
*Lead reportinglimit 5 ppb based on 

### 1987 Drinking Water Standard. Recently lowered lead ?Mercury values questionable due to probable contamination. Wa" indicates not analyzed. standard would require reporting limit 

### of 

### 1.5 ppb.TABLE 12 CONTINUED. MEASURED CONCENTRATIONS IN DRINKING WATER LEACHATES.


### simwD control 1 control 2 tap water EC27 TD27 EC61 TD61 EC82 TD82 EC84 TD84 Nitrate-N (rng/L) 

### CTL TEI 0.06 da 0.04 da 0.08 da 0.02 da 

### 0.03 da 0.02 da 

### 0.03 n/a 0.02 n/a 0.04 n/a 

### 0.03 da 0.02 n/a

Notes: %/a" indicates not analyzed. Instrument settings and samples sizes were chosen to produce reporting limits generally one-twentieth or less of the Drinking Water

### Standards at CTL and one-tenth or less at 

### TEI. That is the reason CTL minimum values 

### are less 

### than TEI's minimum values. For comparison, the U. S.EPA National Primary Drinking Water 

### Standards for inorganics are given here in pg/L (ppb) or mgL (ppm). This listis based on the 1987 Drinking Water Standard found in ANSYNSF 61-1991 Appendix F which was published in May 1991. arsenic 50 ppb barium 1000ppb cadmium 10 ppb chromium 50 ppb lead 50ppb mercury 2ppb selenium 10 ppb silver 

### 50 PPb 

### fluoride 4 ppm nitrate-N 10ppm The Drinking Water Standards have been revised. A copy can be obtained fromthe EPA Safe Drinking Water Hotline at 800-426-479 1Monday-Friday 8:30 am-5 pm EST. The inorganic portion of the December 1992 Standards are shown on the following two pages.December 1992 . 

## Drinking Water Standards and 

## Heafth Advisories
Pago 8



# 11WOHGANICS

Asbestos lfibersn >

### low.

Chlorine dioxide
Chromium (total)

... Mercury (inorganic) Molybdenum stLF 0.006 0.006 f . 

# -

..... T. ...

.. 0.05 F 7 MFL 7 MFL
F2 2 F 0.004 0.004LF 0.005 0.005 LrLLLL 

# -

.. . .-
. F 0.1 0.1 F 1.3

. ' - TT" P 0.2 0.2 ;F 4. :'.4

. ,

F zero TT''

:. 4

.. 0.2.

~ .;. "

.....

:. F 0.002 0.002 '' .... ..

..
-L; 'e.

F 0.1 0.1 F 10

. 10 F1 1 t Ptatur HA'


# -

D -0 - f D

F D .D

F D D :o

O D F
F



# .

..: 0

F F F F F 

# - -. .. .- 0.015 0.015

30 30

4 0.9 0.04 0.04 .1 1

1 1

a. -. 0.2 0.2.

.. ? .._ e.



# . .. 

# ..

...... 0.08 1 1 10' 0.015

4 0.9 0.005 1



# - 0.2
0.2

.t

..

.t .

0.01 0.5 Hadth Advisorlor

I?. 0.01 5 0.0004

. 0.07 0 0.005 3 0.09 0.02 0.0005 1 0.1

0.8 0.005
0.8 0.022 0.12
0.14/ 0.005 0.002 0.0003 0.05 0.005 1.7 0.02 1.6 0.16' 30 0.015

2 0.2 3 0.02 3.3

0.2
0.8

0.01 0.2 0.6 0.003

2
0.6 0.005 2.6

0.1



### .. 0.2

-.

0.002 0.04 0.1 0.002 700 MFL

0.0008 

## -

T

.. 

## -

0,


# -

... t



# -

..

" Copper 

### - action level 1.3 mg.4

Lead 

## - action level 0.015 mg/L

## Drinking Water ,Standardsand 

## Health Advisories

December 1992 Page 9

RADKMlucuoEs
Beta panicle and photon

activity If mmly man-made radionuclides)
Radium 226R28

.. 

# -

.. ::.

. , ..

.. st-

...... ..;:;$:

....... '.:!.' .: :. 

### :.io;m

................ ., , ...... 

### .,o.f&.':. .,:

. i: 

# -
-.
.. ... ..

.... .-

.........

L- p 

# .... 

# .. f 0.0005 0.002 t-L..........
..t.::::

....:+ < ;:

......... :..

...... ... ...... ... : .......... ... ... ............. ...*

F zero 4 mrem

. zero 16 pCin P zero 6 pCiA P:, zero 3M)pcJl P zero 20pQR -I-

... ..
... ...

4 mrem/y



# . - c 22/26 pCiR

170 diA. 

## - - -PC@
tbarium

chromium

lead



### 0.001 0.01 0.1 1 10 Concentration, mg/L 

### 0 Cement27 0 Cement 61 

### 0 Cement 82 A Cement 84

Figure 1. Concentrations of barium, chromium, and lead in acetic acid 

### TUPleachates from the four cements selected for this work. For comparison, the highest, lowest, and mean values for all cements in the PCA study 

### of U. 

### S. and Canadian cements are shown as short vertical bars. Concentrations of other elements are not shown since most are either below detection limits or far below regulatory levels.

# FIGURE 2

.I



# .01



# ,001



# e 0

# ,0001 

# CONCRETE LEACHATE RELATIVE CONCENTRATIONS
1/1Oth RCRA LEACHATE

X 

# P

A
0 

# - - LIMIT

A 

### _1/100th 

### A I 

### e .OF LIMIT



### 0 

## e 

# e 6 

### A A 

# + 

# r

a 

### 1 /1OOOt

### h 

# - OF LIMIT 

# -
0 

# t

0 

# t 0

# FIGURE

# 2a

10

1



### .1



### .01 

# CONCRETE TD84 

# LEACHATES AND 

# ESTIMATES OF EXTREMES

0 

### 0



### A

0 0 

# e 0



### A

0 

### 0 

## U
0 0 

# m

0 WATER 0

P0.35


### 0.3 

## -

0.251



### 0.2

OS1

# 1 -

0.2 0.4 

### 0.6 0.8 1 1.2 1.4 Chromium in TCLP cement extract, mg/L 

### R=0.92

I I I I I


# 1 0 siliceous aggregate dolomite aggregate 

# I Figure 3.



# 0.351 0.3 - 0.25- 0.2 - 0.1 5-
0.1 - 

### 0.05- 

### a

0 R=0.89 

## of I I I I I I I 

### 20 

### 40 

### 60 80 100 

### 120 140 160 1 Total chromium in cement, mg/kg 10

0 siliceous aggregate H dolomite aggregate ~~~ 

## Figure 4.

## B 0.02 

## - a Q) 0 

### 0.018- 

# 3 0.016- 

# e 0.014- c 0 

### 0.012- H 0 0



## 3 0.01 I I I I 

### 0 

### 0.004 

### 0.008 0.012 .016 .02 Lead in TCLP cement extract, mg/L 

# I 0 siliceous aggregate dolomite aggregate 

## Figure 5.

0.026 I 

### I 0 

### 0.024

### - 0.022

## - 0.02 

## - 0.01 8- 

### 0.01 6

## - 0.014- 

### 0.012

## - U



### a

0

0 f-. 

### 0.01 

# 1 I I I I 

### 0 

### 0.004 0.008 0.012 0.016 0.02 Lead in TCLP cement extract, mg/L

0 siliceous aggregate dolomite aggregate 

## Figure 

## 6.