Science Applications International Corporation
                Cincinnati, OH  45203
           Contract No. 68
          SAIC Project No.
D1 -0832-03-J1-021 -010
                    Project Officer

                  James S. Bridges
           Pollution Prevention Research Branch
          Risk Reduction Engineering Laboratory
                 Cincinnati, Ohio 45268
               CINCINNATI, OHIO 45268

       The  information  in this document has  been funded wholly or  in part by the United  States
Environmental  Protection Agency under Contract 68-C8-0062 to  Science  Applications International
Corporation. It has been subjected to the Agency's review, and has been  approved for publication as an
EPA document.  Mention of trade names or commercial products does not constitute endorsement or
recommendation for use.

                                                   V \

       Today's rapidly developing and changing technologies and  industrial products and practices
frequently carry with them the increased generation of materials that, if improperly dealt with, can threaten
both public health and the environment.  The U.S. Environmental Protection Agency (EPA) is charged by
Congress with protecting the Nation's land,  air,  and water resources.  Under a mandate  of national
environmental laws, the Agency strives to formulate and implement actions leading to a compatible balance
between human activities and the ability of natural systems to support  and nurture life. These laws direct
EPA to perform research to define our  environmental problems, measure  the impacts, and search for

       The Risk Reduction Engineering Laboratory is responsible for planning, implementing, and managing
research, development,  and demonstration programs to  provide an authoritative, defensible engineering
basis in  support of the policies,  programs,  and  regulations of  EPA with respect  to drinking water,
wastewater, pesticides, toxic substances, solid and hazardous wastes, and Superfund-reiated activities. This
publication is one of the products  of that research and provides a vital communication  link between the
researcher and the user community.

       The  Pollution Prevention Research Branch of the Risk Reduction Engineering Laboratory has
instituted the Waste Reduction Evaluations at  Federal Sites (WREAFS) Program to identify, evaluate, and
demonstrate  pollution prevention opportunities in industrial, military, and other operations. This report is a
pollution prevention assessment of the U.S. Department of Agriculture's Beltsville Agricultural Research
Center.                                       :                •
                                                           E. Timothy Oppelt, Director
                                                           Risk Reduction Engineering Laboratory


       This report summarizes work  conducted at the U.S. Department  of Agriculture's  Beltsviile
Agricultural Research Center (BARC), Beltsviile, Maryland under the U.S. Environmental Protection Agency's
(EPA) Waste Reduction Evaluations at Federal Sites (WREAFS) Program. This project was funded by EPA
and was conducted in cooperation with Department of Agriculture officials.

       The purposes of the WREAFS Program  are to identify new technologies and techniques for
reducing wastes from industrial processes used  by federal agencies and to enhance the adoption of
pollution prevention through technology transfer.  New techniques and technologies for reducing waste
generation are identified through pollution  prevention opportunity assessments  and may be further
evaluated through joint research, development, and demonstration projects.

       A pollution prevention opportunity assessment, which identified areas for waste reduction at BARC,
was performed during the spring of 1991. The study followed procedures presented in the EPA Waste
Minimization Opportunity Assessment Manual (EPA/625/7-88/003).

       Two specific processes, high performance liquid chromatography (HPIC) and the Kjeldahl nitrogen
determination were targeted for this assessment. Several procedural changes were considered for each
as pollution prevention options.   For Kjeldahl, there were also options involving automated equipment
available.       Additionally, pollution prevention could be achieved by scheduling workload and sharing
equipment, particularly when micro-analysis is desired.          •

       While this report attempts to provide viable pollution prevention ideas related to laboratory research,
it was written from a pollution prevention perspective. The perspective of laboratory researchers is often
different, with the, success of their research being their prime focus.  There is middle ground between these
two viewpoints that will allow research work to proceed efficiently while simultaneously reducing the amount
of hazardous waste generated.

       This report  was submitted in fulfillment of Contract No. 68-C8-0062 by SAIC, Inc., under the
sponsorship of the U.S. Environmental Protection Agency. This report covers a period from January 31,
1991, to September 30,1992.

                                   TABLE OF CONTENTS

Section           .                                       .

Disclaimer	        jj

Foreword	       iii

Abstract	 . .	       iv

Tables	       vi

Acknowledgements	       vii

Introduction	        -\

Site Description	'.	       2

Assessment	       3

Feasibility Analysis	-....'	       IQ

Recommendations  	•.	       20
Conclusions	'.	;	       21

Bibliography	       23

Appendices (Worksheets)		       24


Number                                                                            Page

1 Hazardous Waste Streams At BARC	       3

2 Examples of Source Reduction and Recycling Options	       6

3 General Pollution Prevention Options for BARC	       8

4 TKN and HPLC Pollution Prevention Options  .	      20

       The authors wish to acknowledge the help and cooperation provided by David Prevar and Caroline
Roe of BARC's Safety, Occupational Health, and Environmental Section (SOHES).  Other BARC employees,
including researchers, were also very helpful and cooperative. The authors further acknowledge information
provided to us by vendors of equipment and services, and other scientists working in this field.


        This report summarizes a pollution prevention opportunity assessment that the U.S. Environmental
 Protection Agency (EPA)  conducted with U.S. Department of Agriculture (USDA), Agricultural Research
 Service  (ARS) Beltsville area, and  the  Beitsvilie Agricultural Research  Center  (BARC) at the  Beltsville
 Agricultural Research Center (BARC) in Beltsville, Maryland.  EPA efforts  at BARC are part of its on-going
 Waste Reduction Evaluations at Federal Sites (WREAFS) Program. This  project  was funded by EPA and
 was conducted in cooperation with Department of Agriculture officials.  EPA has focused this effort on
 identifying and developing management protocols as well as technical changes that might reduce waste at
 BARC.  EPA has developed this report to describe pollution prevention techniques that may be applicable
 to other governmental and industrial facilities.

 Purpose                                     '

        The purpose of the WREAFS Program is to identify and promote  use of pollution prevention
 techniques and technologies through technology transfer.  Under the WREAFS  Program, EPA identifies
 innovative pollution prevention techniques/technologies through an initial opportunity assessment for a
 specific process or operation.  EPA may then evaluate various prevention opportunities and alternatives
 through research,  development, and demonstration (RD&D) projects.  In the past, EPA has initiated and
 conducted both individual and joint RD&D projects that investigate pollution prevention alternatives. EPA
 then provides the results of these projects to both the public and private sectors through various technology
 transfer mechanisms, including: project reports, project summaries, conference presentations, workshops,
 and EPA information clearinghouses, libraries, and document  repositories.


       As part of the WREAFS Program, EPA assesses  pollution  prevention  opportunities using the
 procedures described in the EPA Waste  Minimization Opportunity Assessment Manual.   An opportunity
 assessment may consist of the following phases:

       •       Planning and Organization - organization and.goal setting

       •       Assessment - careful review of a facility's operations and wastestreams and the identification
               and screening  of potential options to minimize waste

               Feasibility Analysis - evaluation of the technical and economic feasibility of the options
               selected and subsequent ranking of options

       •       Implementation - procurement, installation, implementation, and evaluation (at the discretion
               of the facility).             .     |.

 Many of the opportunities identified during WREAFS projects involve low  cost changes to equipment and
 procedures that may be employed at other federal facilities or in private industry. These pollution prevention
 opportunities can often be implemented  by the facility without extensive  engineering evaluations.  Other
 opportunities identified during these  projects will require further study before full implementation can be
 realized.  Typically, opportunities requiring further evaluation are those that have the potential to affect the
 process and/or require the use of new procedures or equipment.  In such cases, it may be necessary to
conduct demonstration projects..               ;

       As part of the WREAFS Program, pollution prevention opportunities at were assessed BARC in the
spring and summer of 1991. The assessment team consisted of EPA Risk Reduction Engineering Laboratory
(RREL), EPA contractor staff and BARC  employees.  The assessment team met with representatives of

 BARC's Safety, Occupational Health, and Environmental Section (SOHES) and research to determine the
 goals of the pollution prevention opportunity assessment. At this meeting, the participants decided that the
 assessment would focus on two efforts: a general, facility-wide assessment of hazardous waste management
 practices, and assessments of large volume waste generating operations. Total Kjeldahl Nitrogen (TKN)
 Analysis and High Performance Liquid Chromatography (HPLC) were selected as the two operations that
 resulted in large volumes of waste and might provide opportunities for source reduction.  In addition to the
 assessment at BARC, a post-assessment questionnaire (distributed using the BARC E-mail system) was
 developed to collect additional information.

 Organization of Report
        This report is designed to summarize the findings of the pollution prevention opportunity assessment
 conducted at USDA BARC. Section 2 of this report provides a brief description of the facility as well as the
 operations of concern.  Section 3 of this report describes pollution prevention opportunities  for materials
 management, TKN, and HPLC operations identified through the facility-wide assessment. Section 4 presents
 the results  of the feasibility analysis for  the pollution prevention  opportunities  identified  during  the

 SITE DESCRIPTION                             \

        BARC is among the largest and most diversified agricultural research complexes in the world. More
 than 1,500 ARS employees and approximately 1,000 employees of USDA and non-USDA tenant agencies
 conduct research and/or work at BARC in approximately 900 buildings (300 employee-occupied, others are
 animal and farm support) including research laboratories, greenhouses, barns, poultry houses, shops, and
 offices. The facility covers approximately 7,000 acres of land.

        In initiating  the  pollution  prevention opportunity  assessment,  EPA's first effort focusses on
 understanding those activities that result in waste, the nature of these activities will provide some insight
 into the resulting wastes and pollution prevention  alternatives. Further, EPA uses a summary of the types
and volumes of waste generated to identify those operations of greatest concern that may be amenable to
 pollution prevention  options. As part of the BARC assessment,,therefore, EPA characterized both the site
activities and general types of wastes generated.  Each of these topics is discussed below.

Site Activities

       Approximately 900 of the employees are scientists and technicians who perform laboratory work and
specialize  in a wide range of agricultural, environmental, and land management subjects. Various research
efforts  include:

       »      Animal researchers - study livestock diseases, animal nutrition needs, and animal genetics
              and physiology to  improve the productivity of cattle, poultry, swine, and sheep

       » •    Plant specialists - study means to increase or "achieve greater" crop yields by breeding
              plants that use light and nutrients  more efficiently, that have built-in disease resistance, or
              that are able to cope with marginal growing conditions

       «      Agrarians - develop new methods to fight plant pests and diseases, including use of nature's
              own resources-biological controls and naturally occurring chemicals-that are integrated with
              better cultural methods to safeguard the environment while reducing crop loss

       «      Human nutritionists - study the nutrient requirements for optimal health and identify the
              foods that meet these requirements.^  Others work to ensure that meat, milk, and produce

               reach the consumer with all their natural taste and nutritional value.

BARC's record of accomplishments has made it a leader in diversified agricultural research. These varied
research activities result in various types of laboratory wastes that may pose threats to human health and
the environment.

Waste Generation

        Since BARC  includes a variety of individual laboratories, the majority of wastes are generated in
relatively small quantities as a result of laboratory research. Specifically, BARC research may result in spent
chemicals,  experiment residuals,  and expired shelf-life chemicals used in research efforts.  Further,  most
BARC research activities may include chemical analyses of tissue,  blood, and/or environmental media
samples. These samples, once analyzed also become wastes.  In the past, such research  activities have
resulted in wastes requiring off-site hazardous waste disposal. Table 1 shows the categories and quantities
of waste generated.

       The waste disposal costs for BARC (including asbestos and PCB's) were approximately $423,000
in 1990.  The PPOA  believes that the types and amounts of wastes may provide some opportunities for
pollution prevention initiatives.  These opportunities are discussed in the sections that follow.

                       TABLE  1. HAZARDOUS!WASTE STREAMS AT BARC
                            JANUARY 1, 1990 TO DECEMBER 31, 1990

  Chemical  Groups    	.	:	   Total (Lbs/Gal)

         Acids                                 j       .                    333/407
      • -Bases                                :            .                 73/395
         Pesticides                                                       . 2608/73
         Solvents                              '           ^              2112/2328
         Inorganic Compounds                 ;          '                 1705/400
         Organic Resins, Reactive Residues, and Similar Sludge                152/107
         Alkali Metals and  Hydrides                                            15/4
         Asbestos                                                          455/55
         PCBs                                 ,                            1277/0.3
         Totals	'_	:	.	8730/3769.3	

  NOTES:                                       \                         .

  1. Tenant contributions at BARC are not shown above. Teriant contributions from other federal agencies consist of similar
    chemical groups shown above. Waste quantities generated by tenants are 2316 Ibs and 265 Gal.

  2. The estimated constant used by BARC to convert gallons into pounds is 8.5. Therefore, total annual waste generated by
    BARC and tenant agencies is estimated at 45,338 pounds.

ASSESSMENT                                 :

       The PPOA team focused the BARC pollution prevention opportunity assessment on the hazardous
materials/waste management and two waste generating analytical methods commonly used at BARC,  Total
Kjeldahi Nitrogen (TKN) and High Performance Liquid Chromatography (HPLC). The hazardous materials
handling, usage, and  disposal protocols of BARC was reviewed to identify any opportunities to reduce the

amounts of hazardous waste  generated and disposed.  With respect to two specific waste generating
operations, the use of TKN and HPLC was examined to identify options to reduce wastes.  In both cases,
the PPOA team sought to identify methods that would not limit or hinder current (or required) activities of
BARC and its researchers. The general pollution prevention opportunities that were identified as part of tin's
assessment are described in the section below.  The discussion of general prevention techniques is followed
by the assessment of opportunities with respect to TKN and HPLC.
General Hazardous Materials Handling and Usage

        BARC has already established a program to manage hazardous materials and wastes. Further, the
established  program already  includes many  practices  that may result in reduced waste generation,
decreases in the release  of hazardous materials to the  environment, and/or increased recycling.  This
discussion summarizes the existing program as well as pollution prevention opportunities that might be used
to further reduce wastes at BARC. Specifically,  this document addresses the following topics related to the
reduction of laboratory wastes (in general) at BARC:

        •      Current Management Activities  Aimed at Reducing Waste
        •      General  Pollution Prevention Techniques
        •      Implementation of General Pollution Prevention Alternatives     ;

Current Management Activities Aimed at Reducing Waste

       The BARC Safety, Occupational Health, and Environmental Staff (SOHES) oversees an extensive
hazardous waste management program. SOHES operates 235 satellite collection points at the facility and
two marshalling areas where wastes are stored and consolidated for off-site disposal. SOHES uses the
marshalling facilities to accumulate waste solvents by type (halogenated versus non-halogenated, high-water
versus low-water content).  Further, since individual laboratories generate relatively small quantities  of
wastes, SOHES consolidates lab wastes into lab packs at the marshalling facilities.  Satellite collection points
are located  in  laboratories and operated by researchers with oversight by SOHES   Specifically, each
research institute identifies a  hazardous  waste officer who  is responsible for the laboratory's satellite
accumulation area.  The hazardous waste officer is responsible-for proper use of the collection  point with
respect to storage of hazardous materials prior to  pickup and transport to the marshalling areas, which are
less-than-ninety-day storage areas.

       In addition to coordinating the use of the satellite collection areas, SOHES also promotes  source
reduction and recycling amopg its researchers  through various services, technical assistance efforts, and
reduction-oriented policies.  For example, each research facility  is  encouraged to segregate  motor oil,
batteries, and paper for recycling. Further, SOHES conducts periodic "clean sweep" amnesty programs that
provide laboratories the opportunity to properly dispose of hazardous materials and wastes. SOHES also
encourages exchange of excess chemicals by supporting an electronic mail chemical trading system.  The
system provides a facility-wide list of available excess chemicals for potential use by other  researchers.

       With  respect to  technical assistance, BARC  personnel  have recently sponsored a  site-wide
hazardous waste training course, which  included pollution prevention training.   In addition, all  new
employees are  required to participate in hazardous waste training.  SOHES also provides periodic training
to refresh site personnel on proper waste disposal procedures including packaging of wastes for pickup by
an outside contractor. SOHES personnel are currently developing a check-out procedure so that scientists
who are  retiring or leaving the lab  do not leave  behind waste chemicals  which will eventually require
                                               I    ,

       To discourage generation of hazardous  waste and/or ordering of excess chemicals that are
eventually disposed,  BARC has instituted a charge-back policy to the individual management units within

 research institutes for hazardous waste disposal, this policy may provide an additional monetary incentive
 for pollution prevention.  The incentive to reduce waste will continue to expand as increasing hazardous
 waste disposal costs consume a larger portion of the annual research budget. Such a policy, however, may
 also provide an incentive for researchers to identify and use improper waste disposal techniques.

 General Pollution Prevention Techniques

        During the course of this project, a number of references related to laboratory pollution prevention
 was identified. The American Chemical Society (ACS)'is a leader in studying and promoting methods to
 reduce laboratory wastes. ACS has published two documents that provide useful information:  The Waste
 Management Manual for Laboratory Personnel (1990), and Less Is Better. Laboratory Chemical Management
 for Waste Reduction (1985).  Further, EPA has published a document that describes applicable reduction
 techniques: Guides to Pollution Prevention, Research and Educational Institutions. EPA/625/7-90/010
 (1990).                                        h

        EPA has estimated that the total amount of hazardous waste generated by research/educational
 institutions is from 2,000 to 4,000 metric tons per year, which is less than 1 percent of the national total of
 hazardous waste generated annually. Most of these facilities generate small quantities of a wide diversity
 of wastes, and the types of waste generated may vary over time. The references discussed above provide
 a number of generic "common-sense" approaches to laboratory pollution prevention including both source
 reduction and recycling methods.  Examples of  these methods are provided in Table 2.  In addition, while
 source reduction and recycling methods are generally the preferred waste management technique, treatment
 can be an integral component of any laboratory waste management program.  The American Chemical
 Society's (ACS) Waste Management Manual for  Laboratory Personnel (1990) discusses in-lab treatment of
 hazardous waste that does not require the treater to have a hazardous waste treatment, storage or disposal
 permit.                             ,

 Implementation of General Pollution Prevention Alternatives

        Although there are unique impediments to pollution prevention at laboratory facilities in general,
 BARC can promote pollution prevention concepts through various efforts. The pollution prevention process
 is in the beginning stages at BARC. Initially, BARC personnel must gain a complete understanding of waste
 generating processes at the site.   The  BARC's waste tracking system contains information  on  waste
 generation (by building), yet the system does not report the quantities of wastes generated  by individual
 processes.  Until individual waste streams are identified and quantified, BARC personnel will  be unable to
 determine the full extent of existing pollution prevention opportunities. Additional information will be needed
 to develop any comprehensive pollution prevention program for BARC.

        Even  without this  data,  BARC  could  consider  a number of pollution prevention  initiatives.
 Specifically, BARC could increase its control over the purchase and  use of toxic  materials  through a
 centralized purchasing and warehousing system. Chemical orders are currently sent through a five Service
 Center purchasing departments which are geographically spread out at BARC. Research and purchasing
 personnel are not instructed (or trained) to identify material substitutions (i.e., identify and procure less toxic
 materials).   EPA realizes that procurement personnel  can not order less toxic materials when specific
 materials are requested by researchers.  Responsibility  for identifying less toxic substitutes for  laboratory
 uses lies with researchers.

        Purchasing personnel do not have a procedure to limit or eliminate duplicative orders in an attempt
to avoid stockpiling of hazardous materials that might subsequently require disposal after shelf-life expiration.
Under the current procedure, each laboratory places orders through the purchasing staff without cross-
checking the chemicals currently stocked in other laboratories.  BARC's expansion of the central purchasing
system in conjunction with establishing a central chemical warehouse is one potential solution to this

 Pollution Prevention Techniques   Pollution Prevention Options
 Waste Stream Segregation

 Inventory Controls
 Process or Equipment
 Raw Material Substitution
Segregating hazardous and non-hazardous wastes.

Ordering chemicals in smaller containers in order to reduce on-
site inventory and unused surplus.

Conducting inventory control from cradle to grave on-site.

Providing central warehousing for storage and distribution of
chemicals to minimize excess inventory in individual labs leading
to excess surplus.

Using smaller scale operations including microscaie techniques.
Such microscaie approaches are not universally applicable to all
experiments. Certain reactions, for example, may overheat and
are more difficult to control when using microscaie quantities.

Reducing the: amount of solvent used to rinse equipment.

Modifying specific experiments either by substituting non-
hazardous or less toxic chemicals, using different analytical
equipment, or improving the efficiency of yields.  (Instrumental
analysis can use 1/10 to 1/100 the volume typically used in wet
chemistry techniques.)

Substituting detergents, potassium hydroxide, or sonic baths for
chromic acid ^solutions used to clean glassware.
        .         *      »
Reusing spent solvents in applications where purity standards are
less critical, such as  performing initial cleaning of glassware with
spent solvent: from the final rinse of previous cleaning operations
(cascade reuse).

Using spent acids and solvents on routine maintenance of

Providing all employees with education on pollution prevention.
For example, ^laboratory technicians who manage hazardous
residuals should be trained in  proper waste segregation and
disposal  practices. Researchers should be instructed on the
adverse impacts research activities may have on the environment
and possible strategies to design research projects that result in
minimal waste and release of chemicals to the environment.
problem.  (BARC has looked at this but building an appropriate building, staffing it and concerns over
delivery or pickup are deterrents).  Common laboratory chemicals such as solvents would be available
immediately from a central location and dispensed, in quantities required by laboratory researchers. This
would minimize wastes generated from unused surplus. The central purchasing staff could be augmented
with a pollution prevention procurement official who, understanding chemical acquisition and use throughout
the facility, could attempt product substitution measures. Such practices would involve significant changes
from existing practices and may not be accepted at BARC for site-specific reasons.

        The key to reducing wastes at a laboratory!facility rests in educating the personnel to be conscious
 of the amounts of waste they generate. In general, the chemical user may have some control over the
 volumes of waste produced but may not consider their relatively small individual volume a problem. They
 may not realize that all of the laboratories are contributing a relatively small amount to a cumulatively large
 problem. As such, BARC might focus activities that help to inform its research communities of waste issues
 and steps to reduce individual generation rates.  To institutionalize pollution prevention, BARC SOHES or
 other staff may should consider the options discussed in Table 3.  Tracking also supports completion of
 environmental  reporting, feedback for educational;and awareness purposes and allows closer monitoring
 of the cost of waste disposal.
                                               i                  •  .

        These  efforts would target the implementation  of simple practices which would increase the
 awareness of the individual researchers. By incorporating waste reduction into routine laboratory activities,
 BARC personnel  may succeed in promoting waste reduction in all aspects of the facility. In the long-term!
 researchers must begin to incorporate waste reduction practices  into their experimental design before
 research  is conducted, and to monitor the progress  made in reduced  waste generation throughout the
 progress made in reduced waste generation throughout conduct of the  experiments.

 Total Kjeldahl Nitrogen Analyses

        EPA and  BARC personnel identified the Kjeldahl analyses as a waste generating process that might
 offer opportunities for source reduction.  After conducting the pollution prevention opportunity assessment,
 this report was  developed to summarize the nature of the Total Kjeldahl Nitrogen (TKN) Analysis and identify
 possible pollution prevention alternatives. This section first describes the TKN procedures and then identifies
 some pollution prevention alternatives.


        The Kjeldahl method is a widely  used chemical analysis which  was first described in 1883.  It is the
 standard method  for determining protein nitrogen in grains, meats, and other biological materials. Samples
.are oxidized in hot,  concentrated  sulfuric acid, and  bound nitrogen  is converted to ammonium ion.
 Subsequent steps include treatment with an excess of strong base, distillation, and titration of the liberated
 ammonia.  During oxidation with sulfuric acid, carbon and hydrogen in the sample are converted to carbon
 dioxide and water. Nitrogen present in proteins (amine or amide form) is  converted to ammonium ion
 quantitatively.  When nitrogen  is present in  higher oxidation states (nitro,  azo, and  azoxy groups), a
 prereduction step is required. The oxidation process is enhanced through the addition of a neutral salt, stich
 as potassium sulfate.  This  increases the boiling point of the sulfuric acid and therefore the temperature at
 which oxidation occurs. Catalysts used in the oxidation step include mercury, copper, and selenium. After
 oxidation is complete, the solution is diluted with water and made basic with sodium hydroxide. The solution
 is then distilled, and ammonia is collected in a receiving flask which contains hydrochloric acid.

        Two titration methods are used  to quantify the collected ammonia.   When an accurately known
 quantity of hydrochloric acid is present in the receiving flask, the ammonia is neutralized as follows:
 H+ +  NH3 -» NH4+.  The remaining hydrochloric acid is then titrated with sodium  hydroxide, which allows
quantification of the initial  amount of ammonia  present.  A more direct titration uses boric  acid in the
receiving flask:  NH3 +  H3BO3 -» NH4* + H2BO3".  The borate is then titrated with HCI-  hT + H,BO," -*
H3B03.                                                                                   2   3

        Quantities of reagent used for the Kjeldahi procedure vary based on the nitrogen content of the
sample being analyzed. Samples with low nitrogen content require increased sample size for analysis. Such
samples use macro-Kjeldahl techniques which generate approximately 500 to 600 ml of waste per sample.
Analysis of samples with higher nitrogen  content can be performed with a smaller sample size (i.e.. micro-
Kjeldahl analysis). Micro-Kjeldahl analyses result in 50 to 100 ml_ of waste per sample.
                                               i 7




BARC Options

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       Wastes requiring disposal after  a Kjeldahl  analysis consist of the digest, which is alkaline and
contains metals used as catalysts, and the distillate;which is either acidic or basic. Specific constituents of
a macro-Kjeldahl waste stream generated at one BARC laboratory are as follows:

Macro-Kjeldahl waste:  570 ml_ per sample Alkaline

                      Contents                .               Percent

                      Sodium Sulfate Anhydrous;                   0.96
                      Cupric Sulfate 5-Hydrate i                   0.25
                      Selenium Powder        1                   0.02
                      Sulfuric Acid                                3.83
                      Sodium Hydroxide                          8.60
                      Boric Acid                                  5.37
                      Methyl Red/Methyl Blue/ETOH               0.38
                      Distilled Water           '-                  80.59
                                              :                 100.00

       This laboratory performs approximately 3,000 macro-Kjeldahls per year and generates approximate
450 gallons of waste per year from this analysis. For the entire BARC facility, there is no reliable estimate
available of the amount of waste generated by  Kjeldahl  analyses.  In 1990, BARC's total acid and base
wastestreams were approximately 850 gallons.   l

Pollution Prevention Opportunities

       A number of pollution prevention  options for reducing the wastestreams generated through Kjeldahl
analyses were identified.  In all cases, prevention techniques that consist of established technologies and
management techniques were examined. These options are discussed below.

Automated Nitrogen Analysis

       One total nitrogen method virtually eliminates hydrocarbon waste generation using commercially
available automated systems. These microcomputer based systems oxidize the sample using a cobalt oxide
catalyst and determine the nitrogen content via a thermal conductivity detector.  Nitrogen concentrations
are determined in less than three minutes according to one manufacturer's literature.  Acceptable sample
sizes vary from 1  milligram to 1  gram, depending on nitrogen concentration and sample density.

       The sample is oxidized in a mixture of oxygen and helium over a cobalt oxide catalyst. A packing
of silver salts removes halogens and sulfur, and a;packing of hot copper removes oxygen and converts
nitrogen oxides to nitrogen. The exit gas is collected in a glass bulb and consists of water, carbon dioxide,
nitrogen, and helium.  Three thermal  conductivity measurements are  then performed; on the exit gas, on
the exit gas after passage through a dehydrating  agent, and on the exit gas after removal of carbon dioxide
with  Ascarite™.   There  is a linear  relationship between thermal  conductivity readings  and nitrogen

       This analytical method meets most of BARC's performance  needs with respect to TKN.  BARC
currently uses this type of analyzer for some applications with good results. Further, the Quality Assurance
and Research Division at the USDA Federal Grain Inspection Service  (FGIS) in Kansas City has evaluated
the use of these analyzers as a replacement for classical' Kjeldahl methods.  The general impression of the
USDA FGIS researcher contacted by telephone was that the automatic combustion nitrogen analyzers use
an excellent method which provides  good accuracy and greater consistency than  classical Kjeldahls in

addition to performing analyses faster.  Numerous instruments are available commercially from different
 manufacturers. This method is expected to be approved by the Association of Official Analytical Chemists
 (AOAC) in late 1991  or early 1992.

        In addition to meeting researchers performance needs, these analyzers provide a significant health
 and safety improvement to laboratory workers since the analysis is much faster and uses computer-based
 analysis to reduce worker exposure.  Specifically, with this method, the operator does not handle hot acids
 and bases.  Further,  the process does not generate sulfur trioxide fumes during the digestion process.  Of
 course, the process does require health and safety precautions due to the use of flammable gases with the
 automatic analyzer.                                                      '

        The costs associated with  automated nitrogen analysis may warrant  further  investigation to
 determine the usage scenario most advantageous to BARC. The analyzer equipment cost is estimated at
 approximately  $30,000, and therefore may not be economical for labs performing a small number of
 analyses. Use of a smaller sample size in the analyzer places a greater emphasis  on  laboratory personnel
to produce  homogeneous samples but results in reduced chemical and disposal costs.  For example,
 chemical costs for the automated  analyzer are estimated at $0.65 per sample, compared with $2.85 per
 macro-Kjeldahl analysis.  Disposal costs are estimated to be reduced  by $0.70 per  analysis.  Labor per
 Kjeldahl analysis is estimated to be reduced by approximately 50 percent with the automated system. Waste
 generation is virtually non-existent; however copper; filings and anhydrous chemicals used for water removal
 must be periodically changed (i.e., result in waste which may incur hazardous waste  disposal costs).

Automated Analysis Using the Alkaline Phenate Method

        When used  as part of the alkaline phenate method, the automated analysis system provides
opportunities for reduced wastes for protein analyses.  Specifically, the analysis for total nitrogen relies on
the fact that alkaline phenol  and hypochlorite  react with ammonia  to form indophenol  blue that is
proportional to the ammonia concentration.  The blue color formed is intensified with sodium nitroprusside.
BARC researchers currently use this method.
                                              i           •  <
       • Sample digestion with the alkaline phenate method is similar to the classical Kjeldahl, but differing
by the absence of a distillation step. This eliminates the requirement to dilute the digest with water and the
subsequent addition  of base.  Instead, approximately 100 mL of acidic digest are placed  directly into the
analyzer.  Approximately 120 samples per hour can be analyzed automatically, with  the analyzer effluent
estimated at 50 mL per hour or roughly 0.4 mL per sample.  Total waste per  analysis by this process is
estimated to be reduced  by at least 50 percent from that generated by classical Kjeldahl methods.  This
savings consists not only  of reduced digest waste, but also eliminates the requirement to use 50 mL of boric
acid as the receiving  distillation solution.  As with the combustion type analyzer, the phenate analyzer (with
digester) is commercially available at approximately $30,000.  This unit can perform numerous types of
chemical analyses in contrast to the combustion unit which solely determines nitrogen.

Micro-Kieldahl Analysis                    .         .

        Micro-digestion techniques also present BARC  researchers pollution prevention opportunities.
Researchers at BARC indicated that they perform Kjeldahl analyses down to the test tube level (15 mL).
The  method is essentially a small-scaled version of the macro Kjeldahl process.  In such  a  case  the
researcher down scales the sample sizes, reagent materials, instrumentation, and  generated wastes.  The
scale reduction emphasizes a greater  concern for selecting  representative samples and maintaining
consistent testing procedures.  Some BARC analysts view the sampling protocol as a possible impediment
in acquiring reproducible data.

        For other BARC research groups, however, the concern over sample size does  not provide a barrier
to use of the micro Kjeldahl  method.  One analyst commented that several groups  have already begun
                                               10    .     ,.

                                                      \ \

assessing the future switch to the micro method.  An in-house comparison study revealed no major
discrepancies between the macro and micro methods in terms of data quality or performance.  The
advantages of the micro Kjeldahi would seemingly obviate the need for the macro method. This proves to
be valid in cases when a sensitive method of detection is used with the micro TKN.

       Detection plays the major economic factor in implementing the micro Kjeldahi method. In the macro
method, a large sample size generates a concentrated ammonia distillate, from which an aliquot is taken
and titrated.  Good reproducibility is attained since a large volume of titrant is employed. In contrast, the
titration procedure does not suit the micro method. The error generated from titrating a small aliquot is high.
A sensitive detection method, such as the alkaline phenate method, is needed to produce  better results.
Several BARC labs have coupled the micro TKN process to an automated alkaline phenate analyzer. But,
for many groups the equipment costs prohibit the change to  the micro method.

Alternate Catalysts

       BARC researchers may also investigate the use of catalysts in the TKN analysis.  The catalysts of
choice in the classic Kjeldahi method contain mercury and selenium. In particular, the determination of
ammonia with Nessler's reagent should be of concern because of the metcury-based catalyst used in the
method.  BARC researchers proposed copper and titanium to supplant the current catalysts. This would
certainly reduce the hazardous nature of the waste generated.

       In addition, alternatives to these catalytic systems  include the titriometric and potentiometric
methods.  While neither of these substitute methods is as simple to perform as the catalytic method, they
do not require the use of mercury- or selenium-bearing catalysts. Also, researchers might consider using
digestion units which eliminate the need for catalysts during digestion.  For example, one manufacturer
offers a patented, enclosed unit which uses sulfuric acid and hydrogen peroxide for digestion.  Further,
microwave digestion techniques do not require catalysts and  also minimize digestion times.  The process
allows for high temperature and pressure digestions through  microwave  induced  heating. Such methods
might, on a case-by-case basis, be appropriate for some of the analyses performed at BARC.

High Performance Liquid Chromatography (HPLC)            ,

       HPLC is widely used in pharmaceutical and biological research.  HPLC is  estimated to be capable
of analyzing up to  20 percent of  all known  organic compounds, and would potentially analyze 60 to 70
percent of compounds analyzed by BARC researchers (i.e., biological samples).  GC requires compounds
to be relatively volatile and thermally stable,  while HPLC can be used to  perform analyses of low volatility
compounds at room temperature.  HPLC techniques are becoming much more important in the analyses
of environmental samples.  In 1988, EPA formed an HPLC Methods Development Group. This group works
to develop HPLC methods for analytes that cannot be detected currently, and  also to develop better
methods employing HPLC over existing techniques.

       In studying  pollution prevention opportunities,  it  was  determined that there are  numerous
laboratories at the BARC facility undertaking a variety of research oriented problems.  Each lab uses specific
sample preparation procedures and analyses.  Based on comments received from the personal meetings
at BARC and from the HPLC questionnaire, two general  practices were  identified that may provide
opportunities  for waste reduction:  sample preparation and the HPLC analysis. Each of these operations
and related pollution prevention alternatives  is discussed below.

       Laboratories at BARC use HPLC  extensively  in their  research work.   Like other forms  of
Chromatography, HPLC is  used  to separate, isolate, and  identify components of mixtures.   Sample
components separate on a column containing solid adsorbent based on  differing  affinities for the packing
material. The  solvent system carries the sample through, separates the materials in  the column, and washes

 separated fractions off the column. A pump provides the required solvent flow, while sensitive detectors
 identify and quantify eluting  compounds.

        BARC performs many common analyses of biological compounds and matrices. BARC personnel
 routinely analyze such compounds as carotenoids, lipids, vitamins, proteins, amino acids, fatty acids, and
 others. Prior to the use of HPLC, a preparative or extractive procedure is used to isolate a specific analyte
 or a characteristic class of compounds.  This requires the use of organic solvents, such as chloroform, to
 extract or leach the sample  material.

        Sample extraction and HPLC analyses at BARC result in solvent and sample wastes. In 1990 alone,
 BARC personnel  generated  approximately 2,600 gallons of solvent waste. HPLC samples, solvents, and
 sample preparation solvents were significant contributors to this total waste volume.  As such, BARC and
 EPA personnel agreed that techniques to reduce wastes associated with HPLC analyses may play a major
 role in easing BARC's waste disposal burden.    :

 Sample Preparation                          .  ;   .

        The sample preparation step isolates either components of interest or interferents from the sample
 matrix prior to analysis and quantitation by HPLC. ;BARC personnel routinely perform liquid-liquid or liquid-
 solid extraction; extracting aqueous samples with an organic liquid, and solid samples directly with solvent.
 Often, BARC personnel rely upon secondary extractions  of the sample extract or the sample itself.  In
 general, extraction solvents include chloroform, hexane, methanol, and methylene chloride.

       The two basic types of sample preparation ;are analytical (small scale) and preparative (large scale).
 The type  employed depends upon the researcher's specific needs and goals.  As  its  name implies,
 preparative procedures apply to the generation of large quantities (i.e., gram-scale) of material.  This amount
 may be used to  support numerous and varied sample analyses or  to provide a purified component in
 sufficient  quantity.  As such, preparative processes command large sample sizes and solvent volumes.
 Consequently, large sample  wastes are generated.

       In contrast, analytical preparations involve small scale processes, with the primary aim concentrating
 on sample information and identification rather than production. Additionally, these steps and studies are
 usually the precursors to the  preparative stage.  The focus on sample information/identification emphasizes
 the concern of analyte detection and, therefore, of analyte concentration in analytical preparation steps. To
 increase analyte levels, concentration steps are employed.  The  most common involves evaporation to
 dryness and redissolution.  Different concentration factors depend upon the initial and final sample volumes.
 As an example, a sample volume of 10 to 100 L is concentrated to 2 to 3 mL. The resultant factor achieved
 is between one to two orders of magnitude. The higher analyte levels allow for easier detection by HPLC.

       As previously discussed,  BARC  researchers engage in the analyses of varied samples and
 components.  As an example, lipid extraction and analyses are common. The sample preparation step
 proceeds  through sample extraction with chloroform. Afterwards, the analyst distills under vacuum the
 organic solvent, and the redissolves the extract distillate.  The analyst discards the distilled solvent as
 hazardous and proceeds with the HPLC analyses. This example typifies the sample preparation step. The
following sections consider possible pollution prevention ideas to minimize wastes generated from sample

 Source Reduction-
       As a result of this assessment, two source reduction techniques for sample preparation procedures
that might result  in reduced waste were identified.  They consist of solid phase extraction (SPE) and
supercritical fluid extraction (SFE).  SPE utilizes small disposable extraction columns containing sorbent.
Columns are available commercially, and with a variety of sorbent types.  The sample solution is introduced
                                              : 12

to the cartridge (or a filter) and either analytes of interest or interferents are selectively concentrated on the
sorbent.  The bound components can then be eluted off the column using a solvent with a higher affinity
for the analyte than the sorbent. Separation, purification, and concentration of analytes of interest therefore
occur based on the bonded silica chemistry of the sorbent. Cartridge costs range between $1.50 to $3.00

       SPE offers substantial savings compared to typical liquid-liquid extractions through reduced disposal
costs. Estimates of reduced solvent usage by 98 percent are contained in one manufacturer's literature, and
other literature indicates that 1 to 2 mL of solvent and a SPE filter accomplishes the same function as would
200 to 300 mL of solvent used for a direct extraction. While SPE should be useful in reducing wastes for
BARC, its application for pollution prevention is limited to aqueous solutions. Scientists at BARC routinely
use solvents to extract certain constituents (e.g., lipids) from samples. In these instances,  organic solvent
use is required to solubilize or extract the constituents of interest from a sample. SPE in these cases would
only be useful regarding pollution prevention if further component classification or purification is needed.
Clearly,  SPE usage lies in the domain of analytical sample preparation.

       SFE is an innovative technique that offers great promise for replacing chlorinated solvent extractions
in the near future. SFE requires a highly compressed gas above its critical temperature and pressure points.
The gas is thus transformed into a supercritical fluid exhibiting high diffusion coefficients and low viscosities
(relative to a liquid). These properties allow for very efficient transfer of solutes from the sample matrix into
the supercritical fluid.  Carbon dioxide is typically used and modifiers may be added to selectively extract
fractions or compound classes from a sample.  Varying the temperature and pressure (density) of the
supercritical fluid  can  also allow for very selective extractions.  For example, low density CO2 extraction is
similarly to hexane, while higher density CO2 extracts similar to benzene. SFE also offers shorter extraction
times compared to  organic solvents.  After the extraction, supercritical CO2 returns to a gaseous state at
room temperature and pressure.

      . The benefits of SFE have been documented in various journals and trade magazines.  When
extracting hexadecane and  chlorobenzene from diatomaceous earth,  the  Soxhlet extraction required a
20 to 40 gram sample and 300 mL of freon. The analogous SFEjnethod used 2 to 5 grams of sample and
only 6 mL of freon.  Extraction speed was increased with SFE, -a'nd the "cost of the analysis dropped from
$12.50 for the standard Soxhlet extraction to $1.65 for SFE..." Another article states that a Soxhlet extraction
using 450 mL of organic solvent varying  in cost between $1.60 and  $3.00, can be replaced with  SFE
methods at a fluid cost of $0.10. An additional $0.90 per extraction is required to dispose of the Soxhlet
organic solvent, while no disposal costs are involved with SFE. This article further states that assuming an
SFE instrument expenditure of $30,000, and based on an average workload of 150 extractions  per week,
the payback period would be less than 1 M> years.

       Various groups within EPA are currently studying  SFE.   Some EPA environmental laboratory
methods will soon incorporate SFE into analytical methods. While the outlook for SFE looks very positive,
additional research, as well as formal method validation and promulgation  is required before this technique
becomes  universally accepted and used.

       In addition  to the concepts discussed  previously, micro-extraction techniques should be used
whenever feasible to reduce solvent usage and hazardous waste generation.
Recycling-                                     :
       Although  source reduction methods are highly preferred over recycling for pollution prevention
purposes, recycling methods do play an important role. Distillation and reuse of waste organic solvents from
sample preparation procedures may be feasible.  Recycling is an issue of concern for BARC researchers
in that recycled solvents may  not provide purity required for analyses. Currently, however, some BARC
researchers are distilling and reusing these spent extraction solvents. As  such, BARC researchers should

                                               : 13        '   '

 identify those operations where recycled spent solvents can be used.

        The distillation or rotary vacuum evaporation of spent extraction fluids should yield a virtually clean
 solvent for reuse.  The solvent purity is achieved through the differing  boiling points of the solvent and
 impurities.  Since the impurities are biological and tend toward high molecular weights, they should have
 a small or negligible vapor pressure. Conversely, the low molecular weight solvents have much higher vapor
 pressures.  A  simple distillation under vacuum should separate the  solvent cleanly from the biological
 impurities.  A vacuum lowers  the  heat requirements for the distillation and, thereby, minimizes thermal
 degradation and subsequent distillation of biological impurities.  The process could be classified as in-
 process reclamation of the solvents.

        The efficacy of the distillation depends on the spent fluid composition.  A mixture containing solvents
 of similar boiling points yields a clean  but compositibnally impure liquid. As such, spent extraction solvents
 should be bulked and categorized  prior to distillation. This preliminary effort should produce a clean and
 compositionally pure distillate.  The purity of the distilled liquid can be checked by injecting a sample into
 a gas chromatograph (GC) or  by using a refractive index detector.

 HPLC Analyses                            •

        HPLC analyses generate hazardous wastes through the solvents employed as the carrier media.
 This fluid provides the essential  vehicle for sample transport through the HPLC instrumentation. The solvent
 delivery  system pumps the aqueous/organic mixture through the injector, the column, and the detector.
 The resulting effluent is a blend of the sample and the initial influent liquid. Either acetonitrile, methanol, or
 tetrahydrofuran typify the organic  portion of the media.  As such, HPLC effluents are  characteristically
 flammable and, therefore, hazardous.

        Pollution prevention in HPLC begins with an Understanding of how the separation process proceeds.
 The goal of the analyst is to achieve the best separation in the shortest time. To obtain this separation, the
 analyst can optimize the following variables:

               Mobile Phase Composition        ;
               Stationary Phase Composition
               Flowrate                         -
               Column Configuration            i
               Particle Size                      ,

 Each of these factors plays  a significant role in achieving the desired level of separation.  The first three
 variables control the^elution time of the component;(i.e., the time taken between component injection and
 detection). The last three variables control the'width of the peak. As the peak narrows, detection sensitivity
 increases since the signal level rises above the detector's instrumental noise level.  Conversely, as the peak
 broadens, the  analyte signal mires in detector noise.  Further, fast- and slow-eluting  compounds will
 intuitively possess a corresponding narrow and broad peakwidth. The objective is therefore the segregation
 of analytes through time (elution time) and space (peakwidth). This is the goal of a separation.

       The variables affecting the analyte elution time and peakwidth intermingle. The injected analyte has
 a relative affinity for both the mobile  phase (solvent) and the stationary phase (column packing). A stronger
 affinity for the mobile phase yields a short elution time and narrow peakwidth, whereas a stronger affinity
for  the stationary phase yields  a long eiution time and. broader peakwidth.  To separate two or more
 components, their elution times must  be different and their peakshapes  must have  minimal overlap.
Additionally, the analyte exiting  the column must be within a specific concentration range dependent upon
the analyte and the type of detector being used. This ensures analyte detection.

        By manipulating the  parameters, the analyst obtains a separation within the shortest analysis time.
This creates a higher sample throughput since more .analyses can be done in an allotted timespan. Solvent
waste generation is reduced  because the waste volume (column flowrate x run time x number of analyses)
is minimized.

        The following information summarizes HPLC use" at the BARC. The majority of labs employ isocratic
(constant composition mobile phase) elution over gradient (varying compositional mobile phase) elution.
Acetonitrile and methanol are the common organic solvents used to prepare the mobile phase. However,
there are labs using chloroform or methylene chloride as the eluting solvent. Generally, the column flowrates
range from 0.8 to 1.5 mL/min.

Source Reduction-
        HPLC source reduction occurs from the minimization of solvent use.  This impacts several areas,
but in general, focusses on the column processes and the instrumentation involved. As such, this discussion
focuses on the utilization of a column with different dimensions and particulate packing.

        A typical column contains 5 micron packing material and configured at 4.6 mm i.d. x 25 cm length.
Further, the typical column flowrate is approximately 1 mL/min.  By switching to a different column internal
diameter, while holding the  column length and particle size constant, solvent flowrate is reduced and
separation integrity maintained.  The comparisons are shown below:

                                       Fiowrate^ Comparison

                           Column Dimensions.           Flowrate
                         [i.d., (mm) x length (cm)]         [mL/min.]

                                 4.6x25                    1.0

                                 2.0 x 25                  ^  0.2

                                 1.0 X 25                    0.05

Thus, narrowing the column bore effectively reduces solvent consumption. However, modifying the column
configuration creates other effects.  A narrower column (and therefore smaller volume) contains less packing
material.  Consequently, smaller sample sizes (and analyte levels) must be injected to prevent column
overloading.  On the contrary, this may be advantageous since a minimal sample amount reduces waste
at the sample preparation step.

       To increase sensitivity when using a smaller column, the analyst may also choose to reduce the
packing particle  size from 5 to 3 micron. This change enhances sensitivity by narrowing the analyte
peakwiclths.  Further reductions in solvent consumption can then be attained  if the column  length  is
diminished.  A shorter column length produces shorter elution  and analysis times, while still maintaining
adequate resolution.

       The economic feasibility is outlined. Assuming an average laboratory performs 50 HPLC analyses
per month with an average run  time of 20 minutes, switching to a 2.0 mm i.d. column would result in a
reduction of 2.5 gallons  of hazardous waste generated per year. One BARC laboratory conducted  up to
1000  HPLC analyses per month. Use of a smaller column would result in a waste reduction of 51 gallons
per year at this laboratory. With HPLC solvent costs of $50 to 100 per gallon, and disposal costs of $5 to 10
per gallon, the method described above may result in significant economic gains when applied (if possible)
on a facility-wide basis.  If the column  is reduced to a 1 -mm i.d., other changes must be implemented to
retain a required  separation.  The detector cell volume must be minimized from a standard 8 pL to 2-3 //L.
This change is needed because the elution volume of the analyte has been lowered. A lowered detector

                                               15     ••..'-.         V

 cell volume is required to give an accurate portrayal of the analyte peak. Additionally, the injection volume
 must be less than 1 //L  An injection volume greater than 1 //L may change the composition of the mobile
 phase.  This fluctuation affects the analyte elution times.  Both the injection and detector cell volume
 changes are therefore required to maintain optimum sensitivity and peak characterization.

        in summary, BARC researchers might reduce wastes by converting to shorter and narrower bore
 columns containing a 3 micron particle packing for appropriate analyses. The resolution of the separation
 is maintained or increased, while waste volume is depreased. Conversion to a different column configuration
 requires a minimal or zero capital investment, dependent on column bore reduction. The cost of 4.6 and
 2.0 mm i.d. columns incorporating either 3 or 5 micron packings are almost identical. If a 1 mm i.d. column
 is used,  however, the injection loop and detector cell volume must be changed. These conversions require
 a typical investment of approximately $500 to $800, depending upon the instrumentation.

        Communication between researchers may also foster source reduction methods. It was observed
 that numerous  laboratories employ HPLC for analyzing the same constituents. Communication between
 group analysts  may yield valuable information regarding the use of other methods and their analysis speed,
 reproducibility,  accuracy, method detection limit, arid prospective pollution prevention. A rapport between
 the facility HPLC users would facilitate the distribution of knowledge and expertise to all analysts.  Besides
 communication, other source reduction methods for HPLC include:

        •      Preparing only the necessary amount of HPLC mobile phase solvent. Researchers can
               prepare an excess of this solvent  which either is  never used or requires disposal due to
               compositional changes over time.  ,

        •      Stopping the introduction of solvent to the HPLC column as soon as required experimental
               conditions have been met.

        An HPLC separation  can be run  under isocratic or gradient conditions.  An isocratic separation
 means that the mobile phase composition is kept constant during the analysis. A gradient separation occurs
 when a mobile phase constituent, usually the organic modifier (acetonitrile, methanol, THF), is altered during
 the analysis.  At BARC, both types of separations are used.  Isocjatic HPLC wastes, however, are easier to
 recycle and reuse.  The  mobile phase employed in an isocratic mode is always of constant composition.
 Thus, the mobile phase exiting the column is approximately that entering the column. The added difference
 is that the exiting  effluent contains the injected sample mixture.

        "Spent" mobile phase can be reused depending upon the detection method employed.  Typically,
 a sample component is diluted 100 fold after passing through the column. If this waste solvent is used again
for separation, the waste injection analytes will again be reduced 100 fold when they exit the column.  The
 dilution affects  on the original sample multiply to yield a minimal increase in the baseline noise.  This
 approach can generally be used for detection with  a UV-Vis detector. It is, however, not as useful for very
 sensitive detectors such as the fluorescence'detector or with highly absorbing compounds in the UV-Vis
detector. A 10,000 fold analyte dilution may still be detected.

       Alternatively, spent solvent could sequester previously eluted sample analytes prior to reuse by
 passing the solvent  through a "trap" column. The trap column may contain the same support, but with a*
 higher coating of  stationary phase to ensure a high trapping  efficiency. The particle size should also be
large compared to the analytical column. This helps maintain a low backpressure prior to the solvent
delivery system. Overall, this configuration enables the analyst to maintain a closed loop system whereby
the solvent is continuously recycled.  A periodic check on the trap column is advised in order to prevent
contaminant breakthrough.

        Distillation of the HPLC solvent is also a potentially effective procedure to purify solvents for recycle
 and reuse. This is analogous to recycling methods described previously for sample preparation waste
 solvents.   In this case, however, the aqueous  HPLC solvent  would form an azeotropic  (constant
 composition) distillate for reuse.  This liquid should be as pure as the starting solvents (HPLC grade) since
 the biological impurities are non-volatile.   However, with  respect to the initial HPLC fluid, the distillate
 composition may be different.  The addition of fresh solvent to the distillate regenerates the initial HPLC
 mobile phase.

        Distillation and  reuse of the waste HPLC solvent may not be practical in a  research laboratory
 because wide varieties of analyses will be performed and the recycled solvents might be contaminated.  It
 may be more expensive to purify the waste solvent than to buy the new solvents.  For a routine analytical
 laboratory or running large samples of the same analysis, spent solvent recycle and reuse seems ideal.

        As previously discussed, the purity and compositional make-up of the solvent can be checked by
 using the GC or refractive index detector.  This would be beneficial when  solvents have been stored in
 containers over a long period of  time.  Furthermore, the waste  HPLC solvents should be segregated
 respective of the assay.  This separation enables easier and cleaner recycling and reuse. Recycled solvent
 unsuitable for use in HPLC applications could potentially be used in other ways by researchers.  The
 required costs for distillation equipment-and the trap column are minimal. Coupled with the high costs of
 HPLC-grade solvents ($50 to $100 per gallon) and of disposal  ($10 to $15  per gallon), spent solvent
 recycling and reuse seems ideal. However, the required labor costs and solvent purity concerns may prove
 to be significant, and unacceptable to researchers.

        Suggestions described above are genera! pollution prevention concepts that  may or may not be
 applicable to the individual researchers at BARC.  In addition, some researchers may not consider their
 efforts to contribute to waste generation and, thus, are not likely to expend effort and funds on pollution
 prevention. The concepts described above should, however, have broad application to BARC.  The goal
 of any pollution prevention program is to ensure that all facility residents systematically identify whether or
 not they adversely impact the environment. Further, if they do contribute to an environmental problem, they
 know how to resolve it (preferably through source reduction) or who can help them resolve it.

 Future Methods  and Trends-                    '.     '    . •'''•
        There are several methods currently under investigation which would greatly reduce organic solvent
 waste generation from HPLC analyses.  The  method theories, instrumentation, and application of these
 techniques are still  in a developmental stage. SFE has previously been discussed as a method which could
 replace organic solvent extraction. An analogous method with respect to HPLC and SFE is supercritical fluid
 chromatography (SFC).  SFC is in the developmental stage, less advanced than SFE practices, even though
 commercial units are on the market. SFC operation lies between the realms of GC and HPLC. As in SFE,
 the supercritical fluid possesses viscosities between those of liquids and gases.  This provides for a more
 efficient separation of non-volatile compounds when compared with HPLC.  Additionally, SFC can utilize the
 detectors employed in GC. The universal flame ionjzation detector can therefore aid in quantifying difficult
 HPLC components such as carbohydrates, triglycerides, and fatty acids. SFC  is similar to GC; however,
 non-volatile compounds can be separated and detected. By coupling SFE to SFC, a complete sample
 extraction and analyses  may be obtained wherein virtual elimination of organic solvents is attained.

        Capillary zone electrophoresis is another method which would greatly reduce organic solvent usage
from HPLC. This technique involves the use of a high voltage differential between the inlet and outlet of a
 capillary column.  Samples are loaded into a capillary filled with buffer solution.  An electric potential field
 is established causing analytes to migrate at different rates and separate into discrete zones. The capillary
tube length is approximately 100 cm with a diameter of 50 //. This  method has high resolving power and
may replace HPLC as the method of choice for biological assays performed at BARC.  The technique,
however, is not widely accepted at this time as a standard method to replace HPLC.  Acceptance at BARC

 will likely require formal approval by EPA methods committees and familiarity with the techniques by fellow
 researchers.                                    \


 Issues                                          ;

         Waste generating operations at BARC and similar research institutions provide obstacles to pollution
 prevention initiatives.  While a systematic pollution prevention program is only at the beginning stages at
 this facility, there are inherent limitations to any pollution prevention program. Some of these obstacles are
 due to the nature of laboratory research, while others can be solved only by forces outside of BARC's direct
 control.                                         ;

         There are over 150 individual laboratories performing scientific research at this facility. The nature
 of laboratory work results in a large number of small quantity wastestreams being generated.  BARC is
 different from industrial operations where large quantities of a certain waste type are generated, and payback
 periods for pollution prevention initiatives are relatively short given the application of appropriate technology
 (e.g. replacing solvent degreasers with alkaline washers). Conducting an  engineering/scientific analysis of
 ways to reduce each BARC wastestream will not be cost effective, and due  to the small quantities generated,
 there may be little economic incentive for the free market to devise pollution prevention solutions to these
 problems. The limited solution to this problem is that scientists should be trained in the pollution prevention
 ethic.  With such training, scientists can use their specialized knowledge in their research to incorporate
 individualized pollution prevention concepts into each research effort.

         Scientific research presents other unique problems. There is a need for reproducibility of lab results
 over a  long time period, and naturally scientists are  reluctant to entertain changes in accepted procedures.
 Also,  many of these  analyses  are performed according to standard  methods  used nationally and
 internationally.  Deviations from those methods may  cast suspicion on or invalidate their research in the eyes
 of their peers.  Authorities responsible for methods development (EPA, Association of Official Analytical
 Chemists (AOAC),  American Association of Agricultural Chemists (AAAC), etc.) will need to continue to
 develop and incorporate techniques in approved methods that result in reduced waste.  Further, it may be
 useful for these developing authorities to develop a  comprehensive laboratory pollution prevention manual
 that becomes part of their standardized methods.   This manual could include major topics such as solid
 phase  extraction as well as  "trivial"  issues  such as substituting ethyl  acetate for ether, hexane, or
 dichloromethane for cleaning  the grease from ground glass.  Such a manual, however,  would require
 extensive research to define scientifically acceptable methods that result in minimal wastes. The techniques
 recommended in this report as alternatives were developed because they could provide more accurate or
 reliable results while coincidentally resulting in less waste.  Laboratories could benefit from standardized,
 scientifically acceptable methods that were designed with reduced waste as a goal of the development effort!
 Such a method development effort, however^ would require modification of how scientists are taught to
 design  and develop techniques and  research projects.

        Regulatory agencies and governmental policies also present dilemmas for facilities such as BARC.
 Many of the hazardous waste regulations were specifically written for industrial operations, and laboratories
 operate in a different fashion.  The time and expense involved in  securing and maintaining a TSD permit
 prohibits facilities like BARC from conducting simple;treatment operations.  Combined with this issue is the
 reluctance of state and federal regulators to make definitive rulings on such issues as the acceptability of
 elementary waste  neutralization  at BARC.   Compounding the problem is  the  reluctance  of  BARC
 environmental managers to take a proactive approach to resolving waste issues because of concerns about
 possible enforcement action.  As such, BARC personnel are faced with a  choice of increasing hazardous
 waste disposal costs or identifying innovative means  to reduce waste. In cases where BARC personnel have
. begun to address waste issues, their efforts are often frustrated by political and/or technical issues that are

 out of their control. For example, scientists at BARC have developed a fermentation system for degrading
 HPLC effluents but have been unable to determine the environmental acceptability of this method, in terms
 of permitting required and whether degradation products would still be classified as hazardous waste.

        Recycling programs at BARC also face obstacles.  While BARC maintains an active paper recycling
 program, problems involved with transferring excess government property prohibit the facility from receiving
 proceeds which could make the program self-sustaining. Such an impediment may contribute to the demise
 of recycling efforts at BARC. Further, without the ability to capture the economic benefits of recycling, BARC
 personnel are less likely to expand current recycling efforts to include non-classical recyclables.  For
 example, BARC personnel could potentially sell excess chemicals via waste exchanges. However, without
 a  direct gain few personnel might  be willing to put forth the effort.  The Chesapeake Bay Program is
 currently supporting the development of a waste exchange in the Chesapeake Bay area.  Once established,
 this  could be  a  useful avenue for avoiding disposal of excess  chemicals if  selling operations were

        The discussion of waste exchange  keys the issue of transportation issues with respect to moving
 chemicals. This problem is accelerated at BARC in that BARC is divided into eastern and western portions,
 separated by public roadways.  The separation requires  any  movement of waste to be performed by a
 licensed hazardous waste transporter, with packages meeting all DOT requirements. This increases costs
 for transfer of  materials  to the bulking facilities, and even the transfer of surplus chemicals from one
 laboratory to another.  Many of the  regulations affecting BARC support the overall public interest.  Better
 communication between government agencies  would be helpful in alleviating some  of the unnecessary
 problems described  above. One  researcher at  BARC suggested that an  advisory board be established
 including scientists from  BARC and the State of Maryland Department of the Environment.  This would
 facilitate understanding between the two groups  regarding site activities and associated  environmental

        The researchers  themselves present special challenges to pollution prevention efforts.  While
 scientists are certainly savvy enough to foster pollution prevention, some believe that waste generation is
 simply a necessary part of their work that is relatively unimportant:  Other researchers simply do not believe
 it is cost effective for them (or their technicians) to spend time  on recovering small quantities of solvent or
 taking similar steps. The complexity of the hazardous waste regulations makes scientists reluctant to even
 broach the issues of pollution prevention, recycling, etc.

        Lastly, acceptable pollution prevention alternatives may not be received as scientifically acceptable
 by researchers.  For example, during the site visit, EPA and BARC  personnel discussed the uses of
 centralized operations in "service" facilities.  For example, HPLC analyses could be run in a central facility,
 and enough solvent would potentially be generated at this location to make distillation economically feasible!
This concept met with reluctance  from scientists who believe that non-routine analyses need  to  be
 performed under their direct supervision in their individual laboratories.

       The preceding discussion casts a negative picture for pollution prevention at BARC. Although many
 of the issues discussed above may be valid, the generation of  hazardous wastes still exists. The problem
lies in the fact that a variety of small operations may contribute to a  large problem but researchers do not
see themselves as a  major contributor.  As such, the funds  and effort required to  alleviate  generation
 problems are not warranted since the researcher does not view  himself/herself as a major contributor. This
attitude is reinforced by a hazardous  waste regulatory and policy structure that is not sensitive to researcher
needs and often seems to be a counter intuitive approach  to resolving a non-issue.  Whether these issues
are real or not,   pollution prevention  at  BARC may provide  a forum to make  researchers more
environmentally aware while providing BARC a unified forum to challenge or demonstrate inconsistent
regulatory barriers (i.e., current regulations are geared to large-scale industrial generators).

        To bring pollution prevention concepts to the consciousness of all BARC personnel, it is essential
to identify and develop specific demonstration projects that can provide tangible results. Communication,
education, and technology will help to bring about [reductions in hazardous waste propagation. Currently,
the major hazardous waste production at BARC arises from TKN and HPLC analyses.  Viable alternatives
exist which result in waste reduction. These processes and pollution prevention options may provide BARC
with the needed demonstration' of the feasibility and usefulness of reduction  strategies. The usefulness,
however, will be determined by whether or not the  pollution prevention options can meet the technical
criteria for BARC. As such, the following section focuses on the options detailed and their relative merits.

RECOMMENDATIONS                 ;          ,'.'-.

        Table 4 presents the TKN and HPLC pollution prevention alternatives amenable at BARC.  The
options are listed in order of decreasing impact. Thus, for example, the phenate analyzer is perceived as
a better waste minimization effort than the conversion to a micro TKN method. In general, the ranking
system evolves from the  ideal  concept of complete hazardous waste elimination.  Toward  this goal other
factors such as implementation costs were  considered.  The initial discussion analyzes the ease  and
availability of implementing  the various pollution prevention alternatives.  Afterward, a more global view of
waste minimization is treated.
  Pollution Prevention
 Waste Stream
   Nature pf
   PP Option
Net Operating
Cost Savings

 Nitrogen Autoanalyzer

 Phenate Autoanalyzer

 Micro Analysis

 Alternate Catalyst
Acid/base       Equipment,

Acid/base       Equipment

Acid/base       Procedure ;
Metal catalysts
Procedure >






Solid Phase Extraction
Supercritical Ruid
Solvent Recovery
Column/Particle Size2
Procedure ;
Equipment l
30,000 .
— —
20,000 1.5
— —
4,200 0.19
'  Based on literature specifying at least 150 extractions per week

2  Based on one BARC laboratory which conducts 1000 HPLC analyses per month

         The nitrogen autoanalyzer provides the best waste minimization alternative to the TKN procedure
  Virtually all hazardous byproducts are eliminated.  The analysis speed, detection  capability and sample
  throughput surpasses the Kjeldahl analysis.  Other advantages include:  operational ease  minimal space
  requirements, minimum operator involvement, and reduced health and safety concerns  The inclusion of
  the nitrogen autoanalyzer in AOAC methods shoujd provide the necessary impetus for widespread use.

         In terms of cost, the autoanalyzer compares with the phenate analyzer, the micro Kjeldahl and the
  microwave digestion unit.  Estimated costs for the phenate and the nitrogen autoanalyzer approach'$30 000
  The micro Kjeldahl cost proves negligible since effective use couples it with a phenate analyzer Microwave
  digestion units and vessels cost approximately $12,000.  Clearly, only the digestion  unit competes with the
  nitrogen autoanalyzer  in terms of monetary investment.  After assessing method-related  and pollution
  prevention factors, however, the best option is the autoanalyzer.

         In HPLC, the best alternatives for pollution  prevention occur through  wider use  of SPE cartridges
  (where possible)  and narrower, smaller diameter Columns.  Many laboratories commonly  practice both
  source reduction alternatives. Further, the cost of implementing these options is negligible Narrower bore
  columns are equal in price to the standard configuration. When solvent and disposal costs are figured in
  the price of SPE cartridges proves to be minimal.  Overall, the  net effect reduces waste while maintainina
  or exceeding analytical objectives.

         The practicality of SFE and SFC displacing SPE and HPLC, respectively, is  still far off   The
  supercritical techniques are just now emerging as! viable options in industry.  Of the two methods more
  emphasis has been placed on promoting and developing SFE. Instrumentation and  applications  are
  currently available, with EPA-OSW proposing several new SFE methods. For some  laboratories however
  the high cost  ($30,000) presumably limits its use,  The next five years should mark the prominence of
  supercritical techniques.

                                               {                ...
        The previous section focused on the pollution preventipn options for TKN and HPLC identified
 through this assessment.  Although this report documents the assessment efforts at BARC  the ideas and
 actions brought out are applicable to other research and  academic laboratories. The reduction of waste is
 not the primary concern  of the research or academic investigator.  Rather,  the focus concentrates  on
 generating new ideas, new products, and new techniques. All these efforts are buttressed through collected
 data.   Thus, the  question of equipment  cost,  of  analysis speed, and even of waste reduction  prove
 secondary to the analyst.  The foremost question is "Will it give me good data?"

        Supplanting a long-standing method (that works), such as the Kjeldahl, takes time and effort New
 equipment manufacturers provide comparison studies showing comparable or  better results to the existina
 technology. Even this display may not sway the analyst towards the method. The  introduction of a new
 method also presents some difficult questions: "How will the new data compare to the old?" "How lonq will
 it take  to learn?",  and "Are we sure this will address our needs?" The answers are different  for every
 laboratory group.  Further, the timing proves critical. A switch in the midst of a long term project could  be
 deleterious. All these criticisms favor the stability and familiarity  of the proven method.

        Pollution prevention may be slow for TKN.  However, several BARC laboratories currently own and
 utilize a nitrogen autoanalyzer or a phenate analyzer. These instruments should help to assuage criticisms
 and to foster wider use.  The option listed for HPLC analyses should meet minimal resistance  The column
 is being replaced and not the method.  Only a small amount of time is  needed for method development
 In sample preparation, the use of SPE cartridges depends  upon the specific research and analyst  Pollution
 prevention employing supercritical methods are nearing reality, but will most likely meet the same criticisms
.as those discussed above for TKN.               :

        Education and communication play the dominant roles in instituting pollution prevention measures
at BARC and similar research facilities. For BARC and other research facilities, pollution prevention and data
quality objectives for the experimental design method can be obtained simultaneously.  Scientists certainly
know the attributes  of waste segregation and  spent solvent reuse.  By placing more importance and
involving every group member in these initiatives, hazardous wastes can be reduced. The global solutions
indicated  in Table 4 are  certainly within reach.  ^The effective implementation, however, depends on
employees involvement at all levels  including the!bench analysts, safety officials, procurement officers,
managers, and researchers. Further, researchers are the key in that they must ultimately embrace or discard
waste reducing approaches. The researchers, by validating such techniques/technologies play a critical role
in creating an atmosphere where waste reducing technologies are accepted by personnel. With respect to
implementation of new technology, communication with instrument vendors and outside scientists (such as
analytical chemists, academic scientists, etc.) are indispensable in obtaining an objective view and ultimately
providing  information  so that  BARC personnel imight  decide  whether or  not  new waste reducing
techniques/technologies will still provide valid data.  Through communication and education, pollution
prevention measures can effectively be employed to coexist with the requirements of the analyst.

        Finally, a center-wide pollution prevention; option that  must be implemented is that  of detailed
tracking of chemical  purchases, specific users and processes, and quantification of  waste  generation
volumes. Tracking chemical use and correlating  it to waste generation is the key to defining usage patterns
and establishing researcher accountability.

American Chemical Society.  Less Is  Better:  Laboratory Chemical Management for Waste Reduction.
Washington, D.C.  1985.  16 pp.

American Chemical Society. The Waste Management Manual For Laboratory Personnel. Washington, D.C.
1990. 31 pp.

Ashbrook, P. and C. Klein-Banay.  Laboratory Waste Minimization Survey.  University of Illinois at Urbana-
Champaign, Urbana, Illinois. 1991

Guides  to  Pollution  Prevention:   Research  and Educational Institutions.   EPA/625/7-90/010, U.S.
Environmental Protection Agency, Cincinnati, Ohio, 1990, 48 pp.

Kites, R.A., and W.L Budde.  EPA's Analytical Methods For Water:  The next Generation.  Environmental
Science & Technology, 25(6): 998 - 1006, 1991.

Instrumentation '91:  Chromatography. ;ChemicaI & Engineering News. March 18, 1991.  56 - 77.

Katauskas, T., and H. Goldner.  SFE:  Will It Solve Your Lab's Solvent Waste Problems?  R&D Magazine,
March 1991, 40-44.                           !

LesnikE*. The HPLC Methods Development Program: An Overview.  Environmental Lab. April/May 1990,

Newman, A. Analytical Techniques.  Environmental Science  & Technology, 25(8):  1363 -1364, 1991.

Sawyer, C.N., and P.L. McCarty. Chemistry For Environmental Engineering. McGraw-Hill Book Company,
New York, New York, 1978. 531 pp.

Skoog, D.A., and D.M. West. Fundamentals of Analytical Chemistry. Holt, Rinehart and Winston, New York,
New York, 1976.  804pp.

State of Illinois Hazardous Waste Research & information Center (HWRIC) Update (newsletter), Winter 1990-

Weslowski,  Wayne. Laboratory Hazardous Waste Management Workshop.  Illinois Benedictine College,
Lisle, Illinois, 1989. 31 pp.

                                APPENDIX A
                             PPOA WORKSHEETS
Firm 8AIC
                         Waste Minimization
                       Assessment Worksheets
                          Proj. No.
                         Prepared By_S. Soboi

                         Checked By__	

                                                         Page J_ of JL
4* EPA

Begin the Waste Minimization
Assessment Program
[ Uorksneets Usea
• Get management commitment
I Set overall assessment program goals
• Organize assessment program tasK force z
Assessment organization
and commitment to proceea
Select new Compile' process and facility data 4.6,
assessment targets Prioritize ana select asessment targets 10
ana reevaluate Select people for assessment teams 3
previous options Review data and inspect site
Generate options * 11.12
Screen and select options for further study 13
Assessment report of
selected options
• Tecnmcal evaluation 14
• Economic evaluation 15.16.17
» Select options for implementation
x Final report, including
i recommenoea options
• Justify projects and obtain funding
Repeat the process ' • Installation (equipment) - 18
• Evaluate performance 19
Successfully operating
waste minimization projects

Date 9/20/91
                             Waste Minimization
                           Assessment Worksheets
                        Proj. No._
                              Prepared By S. Sobol

                              Checked By	
                                                         Sheet 1 of 1
                                                                        Page 1 of _1_
4* EPA
                                                                   TELEPHONE #
Program Manager
                 G. Baker
                                     Cincinnati, OH
Site Coordinator
                 C. Roe
                                           Beltsville, MO
                                                        (301) 504-5557
Assessment Team Leader
                 S. Sobol
                                           Paramus, NJ
                                                        (201) 599-0100

Site I3ARC
Date 9/20/91

Waste Minimization
Assessment Worksheets
Proj. No.

Prepared By
S. Sobol

Checked Bv
Sheet 1 of

1 Page

1 of 2

4* EPA
Assessment Team
Site Coordinator
Materials Control
Quality Control

S. Sobol
C. Roe

H. Schovronnek

J. Gutierrez
J. Ho
J. Bridges
D. Prevar
Telephone #

Paramus, NJ/
(201) 599-0100
Beltsville, MD/
(301) 504-5557

Paramus, NJ/
(201) 599-0100

Rockville, MD/
(301) 840-8967
Cincinnati, OH/
(513) 569-7321
Cincinnati, OH/
(513) 569-7683
Beltsville, MD/
(301) 504-5557









        i 26

 Firm SAIC
 Site  BARC
 Date 9/20/91
                                         Waste Minimization
                                       Assessment Worksheets
                                   Proj. No._
                             Prepared By S. Sobol

                             Checked By	
                             Sheet J_ of J_     Page_2_of_2_
 Firm:  Beltsville Agricultural Research Center

                 Building 003 Room 117
 Street Address:   10300 Baltimore Blvd.
 City:  Beltsville
 State/ZIP Code: Maryland 20705
Telephone: (301) 504-5557
Major Products: Scientific research
SIC Codes:
EPA Generator Number:
Major Unit or:
Product or:
Operations:   A large number of individual laboratories conduct scientific research on a variety of agric

  	related topics.                     ;
:acilities/Equipment Age:  Laboratory equipment is modern and in many cases is state-of-the-

Dat« 9/20/91
Waste Minimization
Assessment Worksheets
Proi. No.
Prepared By S. Sobol
Checked By
Sheet 1 of 1 Page 1

of 1
Total Staff
Scientists and Technicians
Direct Supv. Staff
Average Age, yrs.
Annual Turnover Rate
Seniority, yrs.
Yrs. of Formal Education
Training, hrs./yr.
Additional Remarks
The facility has a very well educated and highly trained work force consisting of 900 scientists and technicians.

Many of the scientists have doctoral degrees.  Additional personnel at the facility provide support ranging from

administrat ive through facility maintenance.

Date 9/20/91
Waste Minimization
Assessment Worksheets
Pro}. No.
Prepared By S. Sobol
Checked Bv
Sheet 1 of 1 Page 1 of 1
I Worksheet
I 6
Process Unit/Operation
Operation Type: a
il kieldahl nitrogen analyses
Continuous ' a
Batch or Semi-Batch a

4* EPA
Process Flow Diagram
Material/Energy Balance
Flow/Amount Measurements
Process Description
Operating Manuals
Equipment List
Equipment Specifications
Piping & Instrument DIag.
Plot and Elevation Plan(s)
Work Flow Diagrams
Hazardous Waste Manifests -
Emission Inventories
Annual/Biennial Reports
Environmental Audit Reports
Permit/Permit Applications
Batch Sheet(s)
Materials Appl. Diagrams
Product Composition Sheets
Material Sfaety Data Sheets
Inventory Records
Operator Logs
Production Schedules
; Status '










Y ;





Used in this











Date 9/20/91
Waste Minimization
Assessment Worksheets
Pro). No.
Prepared By S. Sobol
Checked By
Sheet 1 of 1 Page 1 of 1
Name/ID j
Component/Attribute of Concern
Annual Consumption Rate
Component(s) of Concern
Purchase Price, $ per 	
Overall Annual Cost
Delivery Mode2
Shipping Container Size & Type3
Storage Mode4
Transfer Mode3
Empty Container Disposal/Management0
Shelf Life
Supplier Would
- accept expired material (Y/N)
- accept shipping containers (Y/N)
- revise expiration date (Y/N)
Acceptable Substitute(s), if any
Alternative Supplier (s)
Stream No. 	
TKN analyses
Chemical supply companies
H,SO,, NaOH, metal catalysts

Unknown facility wide

Glass bottles
] ' S



Stream No._




Stream No..

1 stream numbers, if applicable, should correspond to those used on process flow diagram.
2 e.g., pipeline, tank care, 100 bbl. tank truck, truck, etc.
3 e.g., 55 gal. drum, 100 Ib. paper bag, tank, etc.
4 e.g., outdoor, warehouse, underground, aboveground, etc.
5 e.g., pump, forklift, pneumatic transport, conveyor, etc.
6 e.g., crush and landfill, clean and recycle, return to supplier, etc.

.Site 13ARC
Date 9/20/91
Waste Minimization
Assessment- Worksheets
Proi. No.
Prepared By S. Sobol
Checked By
Sheet 1 of 1 Page

1 of 1

Component/Attribute of Concern

Annual Production Rate
Component(s) of Concern

Annual Revenues, S

Shipping Mode
Shipping Container Size & Type
Onsite Storage Mode x
Container Returnable (Y/N)
Shelf Ufe
Rework Possible (Y/N)
Customer Would
- relax specification (Y/N)
- accept larger containers (Y/N)

Stream No.
TKN analyses

Acidic and basic
wastes containing

Unknown facility



Stream No.


Stream No.

stream numbers, if applicable, should correspond to those used on process flow diagram.

Data 9/20/91
Waste Minimization
Assessment Worksheets
Proj. No.
Prepared By S. Sobol
Checked By
Sheet 1 of 4 Page 1

of 1

4* EPA
1. Waste Stream Name/ID: TKN analysis wastes Sirnjur, Number
Process Unit/Operation
 Waste Characteristics (attach additional sheets with composition data, as necessary)
 a gas         a liquid       o  solid       o  mixed phase
        Density, Ib/cuft	      High Heating Value, Btu/lb   No
        pH acidic and basic      Flash Point    	
 Waste Leaves Process as:
                                                                           Water High
a air emission a  waste water a  solid waste a hazardous waste
n continuous	
H discrete After completion of each analysis       	_^
                 discharge triggered by
                            a chemical analysis.
                            n other (describe)
              D  periodic.
                            a  sporadic (irregular occurrence)
                           "o  non-recurrent
length of period:.
Generate Rate
                                                              Ibs per year,
                                                              Ibs per	
                                                              Ibs per	
                     Batch Size
                                                              batches per
                                                            . average.
*There is no accurate estimate for quantities of this waste generated facility wide. One rough guess Is over 1 ooo
gallon* per year.

Firrn SAIC
Date 9/20/91
Waste Minimization
Assessment Worksheets
Proj. No.
Prepared By S. Sobol
Checked By
Sheet 2 of 4 ' Page 1 of 1
6.     Waste Origins/Sources
      Fill out this worksheet to identify the origin of waste.  If the waste is a mixture of waste streams fill
      out a sheet for each of the individual waste streams.

      Is the waste mixed with other wastes?       n Yes a No

      Describe how the waste is generated.

      Classical kjeldahl analysis requires digestion with sutfurie acid (including metal catalysts!, dilution

      of the digest with water, followed bv addition of base. After distillation. tJtratlon i« required for

      nitrogen present.  The digest and distillate are disposed as hazardous waste.     	
     Example:     Formation and removal of an undesirable compound, removal of an unconverted
                  input material, depletion of a key component (e.g., drag-out), equipment clearing
                  waste, obsolete input material, spoiled batch and production run, spill or leak
                  cleanup, evaporative loss, .breathing or venting losses, etc.

Date 9/20/91
Waste Minimization
Assessment Worksheets
Proi. No.
Prepared By S. Sobol
Checked By

. Worksheet

        Waste Stream TKN Analysis
Management Method
Leaves site in a bulk
                     n  roll off bins
                     B 55 gal drums
                     a  other (describe)
       Disposal Frequency   Accumulates in satellite collection points, bulked at marshalling facility, and
                            disposed as necessary	  •
       Applicable Regulations1
                           RCRA, State of Maryland regulations
       Regulatory Classification2    Characteristic waste due to corrosovitv
       Managed      a onsite            a offsite
                     H commercial TSDF   __.	
                     n own TSDF	
                     n other (describe)	
             o  direct use/re-use	
             n  energy recovery	
             a  redistilled	
             D  other (describe)   	
             reclaimed material returned to site?
             a  Yes B No  a used by others
               residue yield	
                       residue disposal/repository.
Note1  list federal, state & local regulations (.e.g, RCRA; TSCA, etc.)
Note2  list pertinent regulatory classification (e.g., RCRA-Usted K011 waste, etc.)

Date 9/20/91
                                     Waste Minimization
                                   Assessment Worksheets
                               Proj. No._
                                                 Prepared By S. Sobol
                                                 Checked By	'.
                                                 Sheet  4  of 4
                                                                -4_of.4_     Page J_ of J_
          Waste Stream TKN Analysis
                             (continued)    "
Management Method (continued)
Treatment          a biological.
                            a oxidation/reduction.
                            a incineration
                            n pH adjustment.
                            a precipitation	
                            n solidification
          Final Disposition
                 a other (describe)	
                   residue disposal/repository.
                 a landfill	
                 n pond	
                            a lagoon.
                           n deep well.
                           n ocean	
                           n  other (describe)
                 Costs as of Fall. 1991   (quarter and year)
Cost Element:
Onsfte Storage & Handling
Transportation Fee
Disposal Fee
Local Taxes
State Tax
Federal Tax
Total Disposal Cost
Unit Price
$ per qal


Reference/Source: ;

BARC disposal contract


Data 9/20/91
Waste Minimization
Assessment Worksheets
Proi. No.
Prepared By S. Sobol
Checked By
Sheet 1 of 1 page 1

of 1
Waste ID/Name:
Component/or Property of Concern
Annual Generation Rate (units 	 )
Component(s) of Concern (per analysis)
Coslt of Disposal
Unit Cost ($ per gal )
Overall (per analysis)
Method of Management2
Priority Rating Criteria3
Regulatory Compliance
Treatment/Disposal Cost
Potential Liability
Waste Quantity Generated
Waste Hazard
Safety Hazard
Minimization Potential
Potential to Remove Bottleneck
Potential By-product Recovery
Wt. (W)

- '

Sum of Priority Rating Scores
Priority Rank
Description1 '.
Stream No.

500-600 ml
(0.15 gal)


2 (RxW)
R x W .

Stream No.


2 (RxW)

> Stream No.






Notes: 1 Stream numbers, if applicable, should correspond to those used on process flow diagrams.
For example, sanitary landfill, hazardous waste landfill, onsrte recycle, incineration, combustion
with heat recovery, distillation, dewatering, etc.
3 Rate each stream in each category on a scale from 0 (none) to 10 (high).

 Finn SAIC
 Sita BARC
 Date 9/20/91
                                      Waste Minimization
                                    Assessment Worksheets
Proj. No._
                            Prepared By S. Sobol

                            Checked By	
                                                            Sheet J_ of J_    Page J_ of J_
4* EPA
Meeting format (e.g., brainstorming, nominal group technique)  Brainstorms

Meeting Coordinator  H. Skouranek	
Meeting Participants S. Sobol. C. Roe. J. Gutierrez. J. Ho, J. Reeves
List Suggested Options'
1. Performs analyses using micro-kjeldahl after
freeze drying sample
2. Neutralize wastes generated
3. Use automated combustion analyzer


Rationale/Remarks on Option
1. Sample volatiles would be lot making analysis
2. May require treatment permit; not true source
reduction; metals present could be a problem
3. May be too expensive and not an official
approved method





Data 9/20/91
Waste Minimization
Assessment Worksheets
Proj. No.
Prepared By S. Sobol
Checked By
Sheet 1 of 1 Page

1 of 1
                                    ; OPTION DESCRIPTION
 Option Name: Automated combustion analyzer
 Briefly describe the option  Instrument bums the sample to be analyzed and nitrogen present Is determined fay
 thermal conductivity method.	      '    	
 Waste Stream(s) Affected: Acid and base wastestreams
 Input Material(s) Affected:  Acid, base, water, metal catalysts
 Produces) Affected:,
 Indicate Type:
                          Source Reduction
                           X  Equipment-Related Change
                          	 Personnel/Procedure-Related Change
                          _ Materials-Related Change
                          Recycling/Reuse  ,
                          _ Onsfte    _ Material reused for original purpose
                          	 Offstte    	 Material used for a lower-quality purpose
                                       _ Material sold
                                       	 Material burned for heat recovery
Originally proposed by; J. Reevea. BARC
         Reviewed by:	
                                  .no,  by:.
Approved for study?   X   yes 	
Reason for Acceptance or Rejection Significant hazardous waste reduction possible


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Dale 9/20/91
Waste Minimization
Assessment Worksheets
Proi. Unit/Oner. TKN
Proi. No.
Prepared By S. Sobol
Checked By
Sheet 1 of 6 Page

1 Of 1

)ption Description Automated Combustion Analyzer
 1.     Nature of WM Option  a Equipment-Related
                             a  Personnel/Procedure-Reiated
                             a  Materials-Related
2.      If the option appears technically feasible, state your rationale for this. Accented and currently used bv
       Is further analysis required?   a Yes B No
       If yes, continue with this worksheet. If not, skip to worksheet 15.
3.      Equipment-Related Option
                                           YES    NO
       Equipment available commercially?   n      a
Demonstrated commercially? ', a a , •
In similar application?
n n :
Describe closest industrial analog

Describe status of development ; '

Prospective Vendor

Working Installation^)

Contact Person(s)

Date Contacted'
; ,

      Also attach filled out phone conversation notes, installation visit report, etc.

Date 9/20/91
Waste Minimization
Assessment Worksheets
Pro|. Untt/Oper. TKN
Pro). No.
Prepared By S. Sobol
Checked By
Sheet 1 of 6 Page 1

. Worksheet

Jtiort Description Automated Combustion Analvzer
  CAPITAL COSTS - include all costs as appropriate.
  a  Purchased Process Equipment
         Price (fob factory)
         Taxes, freight, insurance
         Delivered equipment cost
         Price for initial Spare Parts inventory
  a Estimated Materials Cost
 a Estimated Costs for Utility Connections and New Utility Systems
.  .      Electricity	
        Steam                             _	.	
        Cooling Water	,-"
        Process Water	
        Refrigeration                          :	
        Fuel (Gas or Oil)	
        Plant Air      ,	
        Inert Gas	
 a Estimated Costs for Additional Equipment
        Storage & Material Handling,    -       :     '_	
 C] SHe Preparation
        (Demolition, site clearing, etc.)
 o Estimated Installation Costs
        In-house Staff

Dlite 9/20/91
Waste Minimization
Assessment Worksheets
Prol. No.
Prepared By S Sotjoj
Checked By
Sheet _2_ of _§_ PageJLofJ.
 n Engineering and Procurement Costs (In-house & outside)
        Engineering           ,	
        Procurement                     	_^
'        Consultants	
 a  Start-up Costs
        In-house Staff                    :_    	
 n Training Costs                        .    	
 Q Permitting Costs
       Fees                                 '	
       In-house Staff Costs                           ,
a Initial Charge of Catalysts and Chemicals
                                       per analysis
       Hem #2
n Working Capital [Raw Materials, Product, Inventory, Materials and Supplies (not elsewhere specified])].
       ltem#1                          .	.   .
       Hern #2                          I	
       Item #3                          	    .
       ttem #4
n Estimated Salvage Value (tt any)	

Firm SA1C

Date 9/20/91
Waste Minimization
Assessment Worksheets
Prol. Untt/ODer. TKN
Prof. No.
Prepared Bv S. Sobol
Checked Bv

Sheet _2_ of _&_ Page 1 of 1

Cost item
Purchased Process Equipment
Utility Connections
Additional Equipment
SHe Preparation
Engineering and Procurement
Start-up Costs ;
Training Costs
Permitting Costs
Initial Charge of Catalysts and Chemicals ($0.65 per analysis)
Fixed Capital Investment
Working Capital
Total Capital Investment
Salvage Value



Dalle 9/20/91
Wast* Minimization
Assessment Worksheets
Pro|. Untt/Opor. TKN
Prol. No.
Prepared ByS. Sobol
Checked Bv
Sheet 4 ot_§_ PageJ_

of J_
 a Esrtimated Decrease (or increase) in Utilities
                                41 EPA
Cooling Process
Process Water
Fuel (Gas or Oil)
Plant Air
Inert Air
Unit Cost
$ per unit ;


Decrease (or Increase) In
Unit per time

Total Decrease (or
$ per time

Assume power roquirements are similar to energy consumption used In classical kjeldaW.
INCREMENTAL OPERATING COSTS - Include all relevant operating savings. Estimate thesa costs on an
                                incremental basis (i.e., as decreases or increase over existing costs).
. Quarterly.
. Monthly	 Daily,
a Estimated Disposal Cost Saving
      Decrease in TSDF Fee
      Decrease in State Fees and Taxes
      Decrease In Transportation Costs
      Decrease in Onsfte Treatment and Handling
      Decrease in Permitting, Reporting and Recordkeeping
                   Total Decrease in .Disposal Costs
n 'Estimated Decrease in Raw Materials Consumption
                           $0.70 per macro analysis
aee next page

Unit Coat
$ per Unit

Reduction in Quantity
Units per time

Decrease in Cost
$ per time


Datiu 9/20/91
Waste Minimization
Assessment Worksheets
Prol. Unit/Open TKN
Proj. No.
Prepared By S Sobol
Checked By
Sheet _§_ of .4. Page 1

of 1
 a Estimated Decrease (or increase) in Ancillary Catalysts and Chemicals
H2SO4, NaOH, metal catalysts and other

Unit Cost
$ per Unit

Decrease (or increase)
in Quantity
Units per time

Total Decrease
(or increase)
$ per time

 o Estimated Decrease (or increase) In Operating Costs and Maintenance Labor Costs (include cost of
   supervision, benefits and burden).

   TTm$ to perform each analysis l$ assumed to be cut In half - I.e.. 2.5 mlntrta savings per gna|vsis at S25/hour

   rate =  $1 savings per each analysis in labor.	
 n Estimated Decrease (or Increase) In Operating and Maintenance Supplies and Costs.
n Estimated Decrease (or increase) in Insurance and Liability Costs (explain).
a  Estimated Decrease (or increase) In Other Operating Costs (explain).

n Estimated Incremental Revenues from an Increase (or Decrease) in Production or Marketable By-products

  Rim SAIC
  Site BARC
  Date 9/20/91
                                        Waste Minimization
                                      Assessment Worksheets
Proj. Unit/Oper. TKN
Proj. No.    	
Prepared By S. Sobol	

Checked By	

Sheet jj. of .3.     PageJ_of_L

"       (continued)
                  Decrease in Operating Cost or Increases in Revenue are Postitivo.

                  Increase in Operating Cost or Decrease in Revenue are Negative.
Operating Cost/Revenue Item
Decr»ase in Disposal Cost
Decrease in Raw Materials Cost
Decrease (or Increase) In Utilities Cost
Decrease (or Increase) in Catalysts and Chemicals
Decrease (or Increase) in O & M Labor Costs
Decrease (or Increase) in O & M Supplies Costs
Decrease (or Increase) in Insurance/Liabilities Costs
Decrease (or Increase) in Other Operating Costs :
Incremental Revenues from Increased (Decreased) Production
incremental Revenues from Marketable By-products
Net Operating Cost Savings
$ per analysis

Note: Jsavings shown are per macro-TKN analysis.


Date 9/20/91
Waste Minimization
Assessment Worksheets
Proj. Unft/Oper. TKN
Prol. No.
Preoared Bv S. Sobbl
Checked By

Sheet 1 of 1 Page 1 of 1
      Total Capital Investment ($) (from Worksheet 15c)   $30.000
      Annual Net Operating Cost Savings ($ per analysis) (from Worksheeet 15f)  $3.90
      Payback Period (in years) =      Total Capital Investment
                            Annual Net Operating Cost Savings
Working backwards, it is assumed a three year payback period would be 'acceptable.* If 210 analyses were
performed per month, cost savings over a three year period would amount to the capital investment of
approximately $30,000.