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APPENDIX C

CDM Technical Memorandum

ROUX ASSOCIATES, INC. MOoeeMn.IBS/ARC

CDM1331 17th Street, Suite 1200Denver, Colorado 80202Phone: 303-298-1311Fax: 303-293-8236

TECHNICAL MEMORANDUM

TO: Jorge Garcia, Solatia Inc.

FROM: Rick Chappell, Roger Olsen, CDM/Denver

DATE: March 29, 2002

SUBJECT: Arsenic Evaluation - Industri-Plex Site, Wobum, Massachusetts

Introduction

This technical memorandum (TM) provides an evaluation of arsenic concentrations ingroundwater samples collected from the Industri-Plex Site (Site) in Woburn, Massachusetts. Theobjective of the evaluation was to characterize and determine the source of the observed increasebetween dissolved and total arsenic (As) concentrations. Specifically, statistical evaluations wereperformed to test the hypothesis that the increase between dissolved and total As is actually dueto the digestion/dissolution of suspended solids during the analytical procedure. That is, theincrease in total concentrations is an artifact of the analytical procedure. Given the groundwatervelocities and presence of fine-grained aquifer material at the site, only the dissolved portion ofthe As (and some colloidal sized material if present) is mobile and can migrate through theaquifer material (Kretzschmar, et al., 1997; Kretzschmar, et al., 1994). Given the hydrogeologicalconditions at the Site, the suspended material (which results in the high total values) is not mobileand does not migrate in the aquifer. Therefore, evaluations related to the nature and extent of theAs contamination should be based on dissolved concentrations and not on total concentrations.The above discussions are visually illustrated by the following diagram.

0.001 0.01 0.1 0.45 1 10 100

-Dissolved

Microns

-Colloidal- -Suspended-

-Turbidity Causing- -Settleable-

-TDS- -TSS-

The diagram illustrates the sizes of particles that can be found in groundwater samples. The firstline below the diagram provides the theoretical or defined size of dissolved, colloidal andsuspended particles. The bottom line provides the operational or analytical determined sizes ofparticles in groundwater samples. In practice, the samples are filtered using a 0.45 micron filter.Contamination and particles in the portion that passes through the filter is operationally called the"dissolved" fraction or "total dissolved solids" (labeled TDS on the line). Contamination andparticles that do not pass through the filter is operationally called the "suspended" portion or"total suspended solids" (labeled TSS on the line). Contamination in an unfiltered samplecontains both the "dissolved" and "suspended" portions. During preparation of the samples in thelaboratory, the samples are digested and a portion of the suspended particles is dissolved into theaqueous phase. Therefore, the analytical results for unfiltered samples or "total" concentrationscontain both the "dissolved" and portions of the "suspended" particles. As illustrated in the abovediagram, the filtered sample actually contains all of the theoretical dissolved and most of thecolloidal portions of the contamination. This fraction clearly contains the contamination that canmigrate in the aquifer and should be used in evaluations associated with the nature and extent ofcontamination.

The following sections provide the results of evaluations performed to test the above hypothesisthat the increased As in the total fraction is a result of digestion of the suspended particles ingroundwater samples.

Data Used in the Evaluations

The data used in the evaluations include the results of all groundwater samples collected on theSite from September 2000 to February 2002. The data set consisted of a total of 392 sampleswhich were analyzed for at least one of the constituents used in evaluations contained in this TM(TSS, As, Fe and Al). A summary of the data by constituent is provided below:

ConstituentTSSAs (dissolved) (ug/L)As (total) (ug/L)Fe (dissolved) (mg/L)Fe (total) (mg/L)Al (dissolved) (mg/L)Al (total) (mg/L)

Count (n)3753613602712709188

MinimumND(<3)

ND(<0.2)ND(<0.2)

0.01390.0072

ND(<0.01)ND(<0.01)

Maximum826,00025,474 •23,026

2682,9100.773447

The evaluations were performed on conventional As results and not the As speciation results.

Comparison of TSS grouped by Delta Arsenic

Review of the As results indicate that two types of samples are present:

- Category 1: Samples which have little or no difference between the total and dissolvedconcentrations.

- Category 2: Samples with significant difference between the total and dissolvedconcentrations.

If the difference between dissolved and total concentrations is caused by the suspended solids,then a significant difference in the Total Suspended Solids (TSS) should exist between the

Page 2 of 11

category 1 and category 2 samples. This explanation was statistically tested. The methods usedand the results are discussed in the following paragraphs.

Differences between dissolved and total arsenic (As) concentrations observed in groundwatersamples collected at the site were calculated as follows:

DeltafAs) = TotaLAsi - Dissolved^

The resultant data were then divided into the two categories previously discussed. Category 1was defined as the samples in which the difference in concentrations (Delta(As)) was less than orequal to 10 |ig/L and category 2 was defined as the samples in which the difference was greaterthan 10 |ag/L. The 10 JJ.g/L cutoff for grouping the data was selected because the analyticaluncertainty is approximately 10 Hg/L. A box plot comparison of natural log total suspendedsolids (TSS) grouped by Delta(As) > 10 U£/L and Delta(As) < 10 Jlg/L is provided in Figure 1. Thedescriptive statistics corresponding with the features of the box plots are as follows:

Box Plot StatisticMaximum (end of upper whisker)75th Percentile (top of box)Median ("bar" symbol in box)Mean ("plus" symbol in box)25th Percentile (bottom of box)Minimum (end of lower whisker)Number of Cases (n)

Natural Log TSS (mg/L)DeltaIAsl > 10 ug/L

13.6247.2085.3135.4733.882-2.303

107

Delta(Ast <= 10 ug/L8.5874.4193.1783.2781.917

-2.303255

Note that the minimum values (-2.303) are associated with the samples which haveconcentrations below the detection limits. As shown in Figure 1, the distribution of TSS values isclearly higher in the Delta(A3) > 10 (ig/L group. Student's t-test results support a statisticallysignificant difference in TSS between the two groups (one-tailed p- value < 0.001; completesummary provided in Attachment A). These results indicate that the source of Delta(As) issuspended solids, i.e., the increase between dissolved and total As is actually due to thedigestion/dissolution of the suspended solids during the analytical procedure.

TSS versus Delta Arsenic, Iron and Aluminum

If suspended particles are being dissolved during the analytical digestion procedure, thenincreases in other elements that make up the overall composition of the suspended particlesshould also be observed. Such element will include silicon, iron and aluminum. The observedincrease in these elemental concentrations should also be directly proportional to the increase inTSS. The database was reviewed to determine if these elements were analyzed. Results for ironand aluminum were available for evaluation. The differences between dissolved and total iron(Fe) and dissolved and total aluminum (Al) were calculated in the same manner as describedabove for As:

) - Dissolved(Fe)= Total(Ai> - Dissolved(Ao

Resulting Delta values plotted against TSS are provided in Figures 2, 3 and 4 for As, Fe and Al,respectively. In each case, the data indicate a positive correlation (linear relationship) between

Page 3 of 11

the Delta values and TSS. These results confirm the hypothesis and indicate that the source ofincreased concentrations of As, Fe and Al is suspended solids due to dissolution/digestion ofsuspended solids during the analytical procedure.

Dissolution/Digestion Model

If the source of increased concentrations of As, Fe, and Al is from digestion of the suspendedsolids, then the amount of TSS, the concentrations of As, Fe and Al in the TSS and the actualportion of the TSS that is digested should be reflected in the resultant total concentrations actuallymeasured. Calculations were performed to evaluate this assumption. For the concentrations ofAs, Fe and Al in the TSS, hypothetical background concentrations of As, Fe and Al in aquifersolids were determined from average background soil concentrations for the Eastern UnitedStates (Shacklette and Boerngen, 1984):

ElementArsenicIronAluminum

Background Soil Concentration (ug/g)7.5

25,00057,000

Hypothetical contributions to the total aqueous concentrations of As, Fe and Al due to analyticaldissolution/digestion of suspended solids were calculated by:

BG Glg/g) x TSS (g/L) x DF = BC (Ug/L)

In this equation, BG is the background soil concentration, TSS is the total suspended solidsconcentration in the aqueous sample, DF is the digestion fraction (the fraction of the suspendedsolids that contribute to the total analytical result due to partial digestion of the suspended solidsduring the analytical procedure) and BC is the resultant aqueous background contributionconcentration due to dissolution/digestion of the suspended solids. As shown in Figures 3 and 4,the background contributions for Fe and Al match the slopes of the Delta versus TSS data. Thesefigures clearly illustrate that the TSS or BG concentrations could easily account for the increasein total analytical concentrations observed. This indicates that the source of Delta Fe and Al ispartial dissolution of suspended solids during analysis.

In Figure 2 for As, two dissolution/digestion model lines are shown in addition to the onecalculated for average Eastern U.S. soil As background (7.5 M-g/g). These additional lines are:BG = 20 Hg/g, representing possible hypothetical average site background As, and 100 M-g/g.representing likely elevated concentrations due to adsorption of As from the groundwater ontoaquifer solids at the site. The basis for the 100 )U.g/g concentration is that at the site As is likelyadsorbed onto the surfaces of the aquifer solids, resulting in higher concentrations that are easilyremoved by analytical digestion. The background contribution lines for As (Figure 2) match theDelta As versus TSS slope and the 100 Jig/g line provides a best-fit line through the data. Thisindicates that the source of Delta As is dissolution of suspended solids and adsorbed arsenicduring analytical digestion.

Comparison of TSS grouped by Sampling Method

An evaluation was conducted for Delta(As) and TSS as a function of sampling method. The datawere grouped by either check valve (bailer) or peristaltic pump method. This analysis did notinclude the total database but was limited to "nonstable" cases, i.e., where one or more fieldparameters (conductivity, pH, etc) did not stabilize during purging and prior to sample collection.

Page 4 of 11

Figure 5 shows the Delta(As) comparison in the form of box plots. The descriptive statisticscorresponding with the features of the box plots are as follows:


Natural Log Delta(4S> (mg/L)Check Valve

7.7695.1653.9043.6642.861-6.908

27

Peristaltic6.8543.8882.3541.167-0.689-6.908

51

Note that the minimum value represents samples with concentrations less than detection limits.Student's t-test on the natural log transformed delta values support a statistically significantdifference (one-tailed p-value = 0.0017; complete summary provided in Attachment A).

Figure 6 shows similar box plots for natural log TSS. The descriptive statistics correspondingwith the features of the box plots are as follows:


Natural Log TSS (mg/L)Check Valve

13.6248.7447.5287.4575.5131.099

25

Peristaltic9.8478.1866.6476.6565.7011.099

36

Student's t-test on the natural log transformed TSS values could not support a statisticallysignificant difference (one-tailed p-value = 0.16; complete summary provided in Attachment A).

The results shown in Figure 5 indicate that higher Delta(AS) values result from the use of the checkvalve method; however, though this result is likely due to higher TSS concentrations using thecheck valve method, this could not be supported statistically (Figure 6) indicating that additionaldata would be required to confirm this result for nonstable conditions.

Resampled Well Locations

Four samples collected in the vicinity of the downgradient end of the Site in November 2001indicated relatively high concentrations of TSS and total As. These well locations were resampledin February 2002 being careful to use methods to reduce the TSS. Dissolved and total As wereanalyzed in both the original sample and the resample, along with TSS, the results of which wereas follows:

Page 5 of 11

Arsenic (total) (ug/L)Arsenic (diss) (ug/L)TSS (mg/L)

P1-01-GW-06Nov-01

RNS137

<5.3211,000

Feb-02R2NS

<5.3<5.3315

P1-01-GW-08Nov-0RNS1

43.7<5.32,270

Feb-02R2NS

<5.3<5.3194

P1-02-GW-05Nov-01

RNS1327.1J

145,000

Feb-02R2nS<5.3<5.3248

P1-02-GW-06Nov-01

RNS141

<5.3542,000

Feb-02R2NS<5.3<5.3479

As shown, initially elevated total As concentrations (43.7-141 JJ-g/L) were reduced to belowdetection limit concentrations (<5.3 M-g/L) as the TSS concentrations were reduced. This clearlyindicates that the source of increased total As is dissolution/digestion of suspended solids duringthe analytical procedure.

Conclusions

The results provided in this evaluation strongly support the conclusion that dissolution/digestionof suspended solids during the analytical procedure is the source of the observed increasebetween dissolved and total arsenic concentrations.

References

Shacklette, H. T. and J. G. Boerngen. 1984. Elemental Concentrations in Soils and OtherSurficial Materials of the Conterminous United States. U.S. Geological Survey ProfessionalPaper 1270.

Kretzschmar, R.; K. Barmettler, D. Grolimund, Y. Yan, M. Borkovec and H. Sticher. 1997.Experimental Determination of Colloid Despositions Rates and Collisions Efficiencies in naturalPorous Media. Water Resources Research, Vol. 33, No. 5, ppl 129 -1137.

Kretzschmar, R.; W. P. Robarge, and A. Amoozegar. 1994. Filter Efficiency of Three Saprolitesfor Natural Clay and Iron Oxide Colloids. Environ. Sci. Technol., Vol. 28, pp 1907-1915.

Page 6 of 11

Figure 1. Comparison of TSS for As Grouped by Delta

t/>soW

wW

I ™.0

As Delta > 10 ug/L As Delta <= 10 ug/L

I!oIf

3

I3

< 0.1

0.01

0.001

Figure 2. Arsenic vs. TSS

y ^TH

100 1000 10OOO

Total Suspended Solids (mg/L)

Arsenic (delta) (ug/L) ————Arsenic (BG=7 5 ug/L) Arsenic (BG=20 ug/L) ————Arsenic (BG= 100 ug/L)

Page 7 of 11

10000000

1000000

100000

10000

o5

it

1000

100

10

0.1

0.01

Figure 3. Iron vs. TSS

• * •£/•**.•»«*• *• • * • • • • • * * '**

10 100 1000 10000


100000 1000000

Iron (delta) (ug/L) —— Iron (bg) (ug/L)

Page 8 of 11

1000000 T

o

100000

10000

1000

100

10

0.1

001

0001

Figure 4. Aluminum vs. TSS

10 100 1000 10000


Aluminum (delta) (ug/L) ——Aluminum (bg) (ug/L) I

100000 1000000

Figure 5. Comparison of Delta (As) Grouped by Sampling(Pump) Method

Check Valve Peristaltic Pump

Page 9 of II

Figure 6. Comparison of TSS Grouped by Sampling(Pump) Method

16 T

Check Valve Peristaltic Pump

Page 10 of 11

Attachment A

Statistical Test Results

t-Test: Two-Sample Assuming Unequal VariancesOn Natural Log TSS

MeanVarianceObservationsHypothesized Mean DifferencedftStatP(T<=t) one-tailt Critical one-tailP(T<=t) two-tailt Critical two-tail

As Delta > 10 ug/L5.4727983128.083129781

1070

1437.3877936435.69241 E-1 21 .65558049

1.13848E-111.976691237

As Delta <= 10 ug/L3.2779114623.244364545

255

t-Test: Two-Sample Assuming Unequal VariancesOn Natural Log Arsenic Delta - Unstable

Check Valve Peristaltic PumpMeanVarianceObservationsHypothesized Mean DifferencedftStatP(T<=t) one-tailt Critical one-tailP(T<=t) two-tailt Critical two-tail

3.6641992818.507844936

270

713.0220184960.0017452361.6665990190.0034904731 .993944352

1.16737215818.743543

51

t-Test: Two-Sample Assuming Unequal VariancesOn Natural Log Total Suspended Solids - Unstable

Check Valve Peristaltic PumpMeanVarianceObservationsHypothesized Mean DifferencedftStatP(T<=t) one-tailt Critical one-tailP(T<=t) two-tailt Critical two-tail

7.45663509412.16794855

250

361.0258914140.1558935081 .6882972890.3117870172.02809133

6.6559379244.408036214

36

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