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SAMPLING AND ANALYTICAL PLAN 

F006 WASTEWATER TREATMENT SLUGE 

Owosso Graphic Arts 

Owosso, MI 

October 26, 2004 

Table of Contents 

I. INTRODUCTION AND WASTE DESCRIPTION 

A. Introduction 

B. Engineering Analysis of Waste Generating Process 

IL ANALYTICAL PLAN 

A. Hazardous Waste Characteristics 

1.Ignitability 

2. Corrosivity 

3. Reactivity 

4. Toxicity 

B. Constituents of Concern 

1. Selected Constituents of Concern 

i. Basis of Listing 

ii. Process materials 

iii. Analytical data 

2. Constituents of Concern not expected in Waste 

3. Special Analyses 

C. Selected Constituents of Concern and Analytical Methods 
D. Quality Control Procedures 

1. Field Quality Control 

2. Matrix Spike / Surrogate Spikes 

E. Data Evaluation 

III. Sampling Plan 

A. Temporal Sampling Considerations 

1. Sampling Frequency 

2. Sampling Duration 

B. Spatial Sampling Considerations 

1.Basis for Sample Distribution 

2. Sample Size and Location 

C. Sampling Equipment 

1. Selected Equipment 

2. Decontamination of Equipment 

D. Sample Management 

1. Container Preparation 

2. Chain of Custody Procedures 

E. Qualifications of Sampling Staff 

Figures 

1. Wastewater Treatment System Schematic 

2. Used Nitric Acid Storage Tank 

3. Sodium Hydroxide Storage Tank 

4. Treatment Tank 

5. Filter Press • 

6. Potential Future Filter Press Cleaning Detail 
Tables 

11-1: Constituents of Concern Included in Basis of Listing 

II-2: Constituents of Concern Included in Raw Products 

11-3: Constituents of Concern Identified in Analytical Data. 

II-4: Selected Constituents of Concern 

Appendices 

Appendix A: Material Safety Data Sheets 

Appendix B: Analytical Data 

Appendix C: Use of Total Data in Lieu of TCLP 

Appendix D: Sample Chain of Custody 
I. Introduction and Waste Description 

LA. Introduction 

Owosso Graphic Arts conducts chemical etching of magnesium plates to produce photoengraved dies for 

the printing and foil stamping industries. Nitric acid is used to etch the surface of magnesium plates to 

create the contoured die surface. 

The waste water treatment process was initiated in 1998 and has undergone only minor changes since 

that time. The etching process is connected to a dedicated waste handling system that does not allow 

wastes from other sources to enter the treatment train. Due to the high level of control of materials 

entering the waste system, little variability is expected in the waste generated by the etching process. 

LB. Engineering Analysis of Waste Generating Process 

When the nitric acid is no longer capable of adequately etching the magnesium surface it is transferred 

through hard piping to a wastewater treatment system for neutralization and ultimately discharged to a 

publicly owned treatment works (POTW) under the Clean Water. Act. Approximately 500 gallons of 

nitric acid solution are treated in each batch. 

Neutralization of the etchant (nitric acid) is intended to make the wastewater suitable for discharge to the 

local POTW. A residence time of approximately 12 hours is required to sufficiently neutralize the nitric 

acid solution. Once the reuired pH is achieved, neutralized wastewater is decanted from the treatment 

tank and discharged through the sanitary sewer. 

The neutralization process generates an inorganic calcium based precipitate. This precipitate is collected 

after wastewater is decanted and dewatered using a filter press designed to remove free liquids. The 

resulting dewatered filter cake exits the wastewater treatment system and is collected in totes beneath the 

press. 

As neutralization is conducted on a batch basis, filter cake is also generated as a batch rather than 

continuously. Approximately 0.25 yards of filter cake are generated from the treatment of each batch of 

wastewater. Generally, 1 to 2 batches of nitric acid are treated per day. 

A schematic of the neutralization system as designed by Systems Integration is provided in Figure 1. 

Photographic details of the existing wastewater treatment (neutralization) system at the Owosso Graphic 

Arts facility are provided in figures 2 through 5. 



I.B.i. Raw Materials 

Substrate materials 

Magnesium is the exclusive substrate metal used in the above described etching process. Magnesium 

sheets are currently purchased from Magnesium Elektron North America. The alloy consists of 

magnesium, aluminum and zinc. A material safety data sheet for the magnesium sheets is provided in 

appendix A. 

The magnesium sheets are treated by the manufacturer with a red coating to protect the plates during 

handling and etching. The primary component of the protective coating is 2-Ethoxyethyl acetate (64%). 

The MSDS for this material is provided in Appendix A. 

The coating is removed by dipping the plate in a Trichloroethylene bath. The part flash dries upon 

removal from the bath such that TCE residue does not remain on the plate. 

The magnesium sheets are further protected during handling through the application of a 14% solution of 

Gum Arabic (Appendix A). 

Etchant 

A solution containing nitric acid (pH <1.0) is used to etch the surface of the magnesium to create the die. 

The 67% nitric acid is delivered in bulk and stored in an aboveground product tank on the exterior of the 

building. No cross contamination of the acid is possible due to the fact that the tank is exclusively piped 

to supply acid to the etching process. 

The etching solution is comprised of 20% nitric acid (described above), 5% detergent and 75% water. 

The MSDS for the detergent product used in the etching solution is provided in Appendix B. 

After each use, the nitric acid solution is adjusted with additional virgin nitric acid to maintain the acid 

balance of the solution. The mixture is used until the concentration of metals in the solution becomes 

too great to effectively etch the surface of the magnesium plates. 

Once the nitric acid solution becomes unusable, it is piped to a dedicated tank (figure 2) to await 

wastewater treatment. As no other systems are connected to the nitric acid storage tank, there is no 

potential for cross-contamination of the used acid. 
Neutralization Chemicals 

A 50% Sodium hydroxide solution (diluted with 2,000 gallons of water) is used to neutralize the used 

nitric acid to a pH between 7.5 and 9.0 prior to discharge to the Owosso Sewage Treatment Plant. The 

sodium hydroxide is stored in an aboveground storage tank (figure 3). As no other system is connected 

to this tank, there is no potential source of cross-contamination of the sodium hydroxide. 

Neutralization is conducted in a batch tank (figure 4) by combining metered amounts of the nitric acid 

and sodium hydroxide solutions. 

I.B.ii. Additional Process Details 

Settling and Decanting. 

After the sodium hydroxide solution is introduced to the nitric acid solution in the treatment tank, the 

mixture is allowed to settle for approximately 12 hours to ensure adequate neutralization. When the 

treatment batch has been neutralized to an acceptable pH, the wastewater is discharged to the City of 

Owosso Wastewater Treatment Plant (WWTP). The WWTP staff periodically collects and analyzes 

effluent samples to confirm compliance with discharge requirements. 

Dc-watering 

The saturated precipitate that is formed during neutralization is transferred through hard piping to the 

filter press for de-watering (Figure 5). Once the filter membranes become loaded, the filter press is 

opened and the de-watered filter "cake" is removed. The filter cake is collected in three gondolas 

beneath the press which are subsequently emptied into a lined roll-off container for storage prior to 

disposal. 

Filter maintenance 

Periodically, the press filters require cleaning to remove accumulated wastewater treatment sludge. The 

manufacturer recommends that either of the following methods be utilized for cleaning the filters: 

I. Power washing 

The filters may be power washed to remove deposits of filter cake that collect in the filters. This is 

the method currently in use at Owosso Graphic Arts. The operational considerations of 

containerizing the washwater and disposal cost of washwater as a F006 waste have caused Owosso 

Graphic Arts to consider other practical options for routine maintenance of the filters. 

2. Closed-loop acid wash 

OGA is currently evaluating the potential for installing a closed-loop acid cleaning process for the 

press filters. Once the filter cake is emptied from the press into the gondolas (as described above), a 
10 % solution of muriatic acid would be flushed through the press to dissolve the precipitate residue 

remaining on the filters. 

Once the cleaning process is completed, the muriatic acid solution would be returned through hard 

piping to the neutralization process for pH adjustment in conjunction with the nitric acid used in the 

etching process. A conceptual schematic is provided in Figure 6 below: 
IL Analytical Plan 

H. A. Hazardous Waste Characteristics 

Any listed wastes proposed for de-listing must not meet the definition of a characteristically hazardous 

waste as defined in 40 CFR Subpart C. The generator of the waste must demonstrate through knowledge 

and/or analysis that the characteristics defined in 40 CFR 261.21-24 do not apply to his/her waste. 

II.A.1. Characteristic of Ignitability 

Ignitability, as it applies to solid materials, is defined in 40 CFR 261.21(A)(2) as a material that can 

cause fire through friction, absorption of moisture or spontaneous chemical changes. These materials, 

once ignited, bum so vigorously and persistently so as to create a hazard. 

This waste stream is comprised of calcium based sediments resulting from the pH adjustment of nitric 

acid with sodium hydroxide. The material is not expected to support ignition or experience adverse 

chemical changes when exposed to moisture or friction. 

Characteristic of Corrosivity 

Regulated corrosive wastes are those which are liquid and corrode steel at a defined rate, and those that 

are aqueous liquids that have a pH less than 2 or greater than 12.5. 

The waste proposed for de-listing is a solid wastewater treatment sludge that has undergone de-watering 

such that no free liquids are present. The definition of the hazardous corrosive characteristic cannot 

apply to this waste stream. 

II.A.3. Characteristic of Reactivity 

Regulated reactive wastes include those which react violently with water, generate toxic emissions when 

combined with water. Reactive cyanide bearing wastes may also generate toxic emissions when exposed 

to liquids with a pH >2 or <12.5 or become explosion risks when heated under pressure, exposed to an 

initiating source, or is defined as an explosive by the Department of Transportation rules found at 49 

CFR Part 172.101 

a. The calcium-based waste generated at Owosso Graphic Arts does not react with water in any 

significant fashion 
b. While the waste has been shown to contain small amounts of Cyanide as a byproduct of the process, 

the waste does not react violently when exposed to moderate pH conditions. 

c. The waste is not expected, due to its relatively inert composition, to pose any risk of explosion either 

under pressure or when exposed to an initiating force. 

d. The waste is not included in the DOT regulations found at 49 CFR Part 173 as an explosive material 

of any category. 

IIA.4. Characteristic of Toxicity 

Results of analysis indicate that toxic constituents included in 40 CFR 261.24 are not present in this 

waste stream at concentrations at or above the regulatory limits defined by regulation. The definition of 

a characteristically hazardous waste based on toxicity, therefore, does not apply to this waste stream. 

11.B. Constituents of Concern 

The US EPA recommends that the entire list of Appendix VIII constituents be evaluated to determine 

which of these constituents are reasonably likely to be present in the waste proposed for de-listing. The 

petitioner may use analytical data and knowledge of the waste to determine which of these constituents 

may be present in his/her waste. 

Owosso Graphic Arts has determined through both analytical data and knowledge of raw products that a 

limited number of constituents are likely to be present in the waste. The process for this determination is 

outlined below. 

II.B.1. Selected Constituents of Concern 

11.B.1.i. Basis of Listing 

The basis for which the F006 waste was listed is included in 40 CFR 261 Appendix VII. 

The compounds which are believed to contribute toxicity to F006 wastes are as follows: 
Raw Products used in Process 

The scope of raw products used in the manufacturing and waste generation processes has been evaluated 

and the following constituents have been found to be present in one or more raw materials contributing 

to the waste: 

II.B.1.iii. Analytical Data 

In addition to the use of material safety data sheets and other manufacturer data, historical analytical data 

has been used to define the scope of constituents of concern associated with the waste. The results of 

historical analysis and recent composite sampling for Appendix VIII parameters are attached in 

Appendix B. 
In addition to total analysis for Appendix VIII parameters, the waste has been analyzed for Oil and 

Grease, Acetone, Ethyl benzene, Isophorone, 4-methyl-2-pentanone, styrene and xylenes. 

The constituents identified above standard detection limits in these analytical efforts are as follows: 

11.13.2. Constituents of Concern Not Expected in the Waste 

With the exception of the above constituents, the parameters that are included in 40 CFR Part 261 

Appendix VIII are not expected to be present in the waste stream. This determination has been based on 

evaluation of raw materials used in the process, results of analysis and controls in place at the facility 

that eliminate the potential for non-process materials to be introduced into the system. 

1133.3. Special Analyses 

The EPA recommends that wastes generated from a stabilization process be analyzed using the multiple 

extraction process (ie. conducting TCLP analysis using low, neutral and high pH conditions). 

While this wastewater treatment sludge generated from the neutralization of nitric acid with sodium 

hydroxide may be classified as the result of a stabilization process, total analysis methods are proposed 

rather than multiple pH TCLP procedures. 

Total analysis has been conducted for parameters included in Appendix VIII. When leachability has 

been estimated (ie. dividing total results by 20 to approximate TCLP results), leachable concentrations 

have proven to be extremely low. 
Owosso Graphic Arts, therefore, proposes to conduct total analysis and use the conservative 

approximation advocated by the EPA (Appendix C). The total results and approximated TCLP results 

will be used in calculating risk factors through the DRAS program. 

II.C. Selected Constituents and Analytical Methods 

Based on the above information, Owosso Graphic Arts has selected the constituents outlined below to 

represent the constituents of concern for this waste stream. These represent the parameters for which 

analysis will be conducted in demonstration of the de-listing petition. SW-846 methods will be used to 

evaluate samples for these constituents 
* Estimated Instrument detection limit as defined in method 6010 

** Based on Method 9010B sensitivities 

*** Based on Method 9031 sensitivities 

II.D. Quality Control Procedures 

II.D.1. Field Quality Control 

All samples will be shipped under an appropriate chain of custody to the selected qualified laboratory at 

a temperature of approximately 4 °C or less. Each sample will be accompanied by a trip blank prepared 

by the laboratory. The purpose of the trip blank will be to identify potential contaminants introduced 

during transport of the sample(s) 

II.D.2. Matrix Spike 

A matrix or surrogate spike will be conducted on each sample batch analyzed in order to calculate 

recoveries and determine the accuracy of the analysis. 

II.E. Evaluation of Data 

Data obtained from the sampling as described above and analysis as described in the Analysis Plan will 

be input into the DRAS evaluation software for comparison with EPA de-listing criteria. 

Results of analysis will also be graphically evaluated to identify trends and outliers in the data. Should 

significant differences be identified between sample results for a given parameter, a statistical evaluation 

may be deemed appropriate to verify accuracy and precision of samples. 
III. Sampling Plan 

III. A. Temporal sampling considerations 

III.A.1. Sampling Frequency 

The homogenous character of the petitioned waste has not changed significantly since commencement of 

waste generation in 1998. Future changes in character are not expected due to the fact that raw materials 

and processes are well defined and unchanging. 

Significant variations in waste character over time are unlikely as there are no seasonal or production 

related variations that influence the quality of the waste material. For this reason, a series of four 

sampling events in addition to the previously conducted initial Appendix VILE analysis are proposed. 

The sampling events will occur during the filter press phase of each of four treatment batches. 

III.A.2. Sampling Duration 

Batches of sludge are generated at approximately three (3) week intervals depending upon production 

schedules. The four samples are proposed to be collected over a period of three months to represent the 

potential variability of the waste material over time. 

Basis for Sample Distribution 

The de-watered wastewater treatment sludge is known to be relatively homogenous in nature based upon 

the use of unvarying raw materials, consistent wastewater treatment methodology and the inability for 

non-process related materials to be introduced into the treatment system (ie. closed system) 

The chemical character of the waste is expected to be highly similar throughout the batch of waste 

generated. Based on this property, and the small volume of waste generated in a given batch, random 

sampling was not deemed appropriate. Rather, a systematic sampling procedure that yields a sufficient 

number of discrete samples of a relatively large sample volume (100 gm) is proposed to adequately 

describe the waste generated in the wastewater treatment process. 
Sample Location and Size 

Each gondola contains slightly greater than one-tenth (0.1) cubic yard of waste material when full. (2) 

discrete samples of approximately 100 grams each are to be collected from each of the three containers. 

Although the waste is known to be relatively homogenous, separate discrete samples will be collected to 

represent the waste as it is generated over the length of the filter press (Figure 8). Forty-eight (48) press 

plates are used to de-water the precipitate. The waste collected in two (2) of the gondolas each receive 

filter cake from 18 of the press plates, while the third gondola, due to its orientation, receives filter cake 

from the final 14 •later. 
A composite will be generated from the six (6) discrete samples of the staged material. The composite 

sample will be analyzed by a qualified laboratory for inorganic constituents of concern as defined in the 

Analysis Plan (Part 4). Additionally, a grab sample will be randomly collected from one of the gondolas 

for the purpose of analysis for organic constituents of concerns as defined in the Analysis Plan. 

Sampling equipment 

III.C.1. Selection of Sampling Equipment 

The waste included in the petition is a dense and relatively cohesive off-white powder. Based on the 

physical characteristics of the waste, sampling will be conducted with a plastic, steel or aluminum hand 

scoop or auger. 

111.C.2 Decontamination of Sampling Equipment 

The sampling equipment will be decontaminated using Alconox or equivalent detergent prior to 

collection of the first sample at each sampling event. The homogenous nature of the waste is such that 

decontamination between discrete sampling locations is not deemed necessary. 

III.D. Sample Management 

III.D.1. Sample Container Preparation 

Sample containers will be prepared by a qualified laboratory prior to the sampling event. The laboratory 

will be expected to provide clean and tightly closed sampling containers appropriate to conduct the 

analyses described in the Analysis Plan. 

III.D.2. Chain of Custody 

Discrete samples collected as described in Figure 8 will be transferred under change of custody to a 

qualified laboratory for compositing and analysis. A sample chain of custody is included in appendix D. 

The sampler will relinquish custody of the samples to the laboratory or courier service with a. signature 

and date. 

Qualifications of Sampling Staff 

Samples are to be collected by staff of Owosso Graphic Arts who are operationally familiar with the raw 

materials, process and treatment system (Level 5 certified treatment plant operator) contributing to the 

petitioned waste. Sampling staff will be familiar with sampling equipment, procedures objectives of the 

sampling effort and sample management techniques. 
Sampling staff will have received training required by 29 CFR 1910.120 and be versed in the health and 

safety plan prepared for this project inclusive of potential health concern of the constituents of concern 

thought to be associated with the petitioned waste. 

Reference Documents 

RCRA Waste Sampling, Draft Technical Reference, EPA 530-D-02-002, 2002 

Index to EPA Test methods, EPA Region New England Region I Library, 2001 . 

EPA RCRA Delisting Program Guidance Manual for the Petitioner; Environmental Protection Agency, 

March 23, 2000. 

SW846; Method 6010B; inductively Coupled Plasma-Atomic Emission. Spectrometry, Revised 

December, 1996 

SW846; Method 9010B; Total and Amenable Cyanide, Revised December, 1996 

SW846 Method 9012A; Total and Amenable Cyanide, Revised December, 1996 

SW846 Method 9031; Extractable Sulfides, Revised July 1992 

SW846 Method 9030B, Acid-Soluble and Acid Insoluble Sulfides, Revised, December, 1996 

SW846 Chapters 1-9; Revised September 1986 through December, 1996