c4t ,,O.L*' DEPARTMENT OF HEALTH SERVICES TOXIC SUBSTANCES CONTROL DIVISION ALTERNATIVE TECHNOLOGY AND POLICY DEVELOPMENT SECTION Application To Study The Reduction Of Arsenic Wastes In The EI ect ro nics Industry AB685 Grant Program
Grant Number 85-001 78
APRIL 1987
Envirosphere Company in cooperation with
Hewlett-Packard Company envirosphere company A Dwsto-ol EbASCO SERVICFS INCORPOfiATEO
3000 W MacArthur Blvd , Santa Ana. CA 92704. (714) 662-4050
April 30, 1987
Mr. Frank Mele Department of Health Services Toxic Substances Control Division A1 ternative Technology and Pol icy Development Section 714/744 P Street Sacramento, CA 95814 SUBJEbT: DRAFT FINAL REPORT FOR GRANT NUMBER 85-00178: THE REDUCTION OF ARSENIC WASTES IN THE ELECTRONICS INDUSTRY
Dear Mr. Mele: Envi rosphere Company in cooperation with Hewl ett-Packard Company is pleased to submit eight (8) copies of our draft final report for the study of arsenic waste reduction in the electronics industry. This project has represented a unique study opportunity because Hewl ett-Packard Company has made available for investigation a full-scale manufacturing process. Ms. Gai 1 Brownel 1, Project Director and Faci 1 ity Envi ronmental Engineer, Hewlett-Packard Company, San Jose, California, acted as official liason with various manufacturing personnel so that each process step producing arsenic could be tested. In many cases, Hewlett-Packard personnel interrupted their normal work process to accommodate the conduct of our project. The Project Staff wish to acknowledge the positive direction and management under your charge that we have received from the Department's A1 ternative Technolgy and Policy Development Section.
Implementation of the findings of our study will allow for the following: o Recycling of gallium arsenide o Substantial elimination of arsenic transport to a hazardous waste landfi 11 -
Mr. Frank Mele Page 2 April 30, 1987
In conclusion, we feel that Envirosphere, Hewlett-Packard, and the Department have worked well together. We look forward to working together again for the Step I1 Application and for our Step I Solvent Reduction Appl ication.
Sincerely,
Richard L. JeGklns, Ph.D, P.E. Project Manager RLJ/mjo SELECTED GALLIUM ARSENIDE CHIP MANUFACTURING PROCESS STEPS
YSTAL- Crystal Growth t LFER 1 %Seed crystal OCESS Encapsulant:fie materialsCrystal
0 He8!C +o POI
Wafer Slicing 2 Diamond blade
Wafer Polish i ng - Polished 3 Materials
Wafers 6 1 b I1 I 6
II
- IAXIAL- Liquid Phase 'P Epitaxial 1 rsElectrical Testing 2
sler Chip Dicing 3 Diamond blade
Wafer EXAMPLES OF GaAs PRODUCTS
GaAs Materials Photo-sensors. Photo-couolers
Hall-sensors, FETs
f PROJECT ABSTRACT
The ga ium arsen de (GaAs chip manufacturing process at Hewlett-Packard Company's San Jose Facility was used as a model to study the reduction of arsenic waste in the electronics industry. Although arsenic is produced from some 11 (eleven) different manufacturing steps, ingot grinding and slicing produced approximately 90% of all arsenic waste. For all arsenic waste produced, greater than 95% was found to exist in the particulate form. The findings of this study indicate that a filter in combination with a filter press could recover the vast majority of arsenic from the wastewater stream. In addition to the benefit of recovering a valuable product (GaAs), the arsenic waste which is currently transported as an extremely hazardous waste to a Class I landfill would be reduced by greater than 95%.
i ACKNOHLEDGEMENTS
The Project Team thanks Alan Clark, Production Engineer, for his efforts in providing data on the amounts of waste gallium arsenide generated during Ingot processing. Without Mr. Clark's assistance, our project schedule would have been seriously protracted.
He also want to thank the Hewlett-Packard Manufacturing staff in general for thei r coop erat ion. DISCLAIMER
The statements and conclusions of this report are those of the Grantee and not necessarily those of the State of California. The mention of commercial products, their source, or their use in connection with material reported herein is not to be construed as either an actual or implied endorsement of such products.
t
iii E
TABLE OF CONTENTS
SUMMARY AND CONCLUSIONS Viii RECOMMENDATIONS iX
1 .0 INTRODUCTION ...... 1
2.0 RESULTS AND DISCUSSION 3
2.1 GALLIUM-ARSENIDE MICROCHIP MANUFACTURING PROCESS ..... 3
.2.2 CHEMICAL CHARACTERIZATION OF WASTE STREAMS ...... 7
2.3 ARSENIC CHEMISTRY ...... 16 2.3.1 Elemental Arsenic ...... 16 2.3.2 Compounds of Arsenic ...... 18 2.3.3 Physical - Chemical Aspects ...... 21 2.3.4 Environmental Cycling of Arsenic ...... 23 2.3.5 Health Effects of Arsenic and Compounds ...... 24
2.4 IDENTIFICATION OF POTENTIAL TREATMENT PROCESSES ...... 30 2.4.1 Introduction ...... 30 2.4.2 General Discussion ...... 30 2.4.3 Filtration ...... 36 2.4.4 Precipitation with Sodium Sulfide ...... 45 2.4.5 Solidification ...... 54 2.4.6 Ion Exchange ...... 58 2.4.7 Adsorption by Activated Carbon ...... 61 2.4.8 Adsorption by Activated Alumina. Bauxite and Carbon ...... 65 2.4.9 Arsine Generation ...... 68
I I 2847E iV TABLE OF CONTENTS
2.5 EVALUATION OF THE RECOMMENDED TREATMENT PROCESS-FILTRATION 69
2.6 ENVIRONMENTAL PERSPECTIVE ...... 74 2.6.1 Reduction of Volumes of Arsenic Waste Generated Statewide ...... 79 2.6.2 Acceptability by Industry ...... 79 2.6.3 Transferabi 1 ity to Other Industries ...... 79
REFERENCES LIST OF INVENTIONS REPORTED AND PUBLICATIONS GLOSSARYOF TERMS, ABREVIATIONS, AND SYMBOLS
APPENDIX A - APPLICATIONS TO STUDY THE REDUCTION OR ARSENIC WASTES IN THE ELECTRONICS INDUSTRY - AB685 GRANT PROGRAM CONTRACT DOCUMENT
APPENDIX 6 - STATE OF CALIFORNIA ENVIRONMENTAL AND HEALTH AND SAFETY REGULATIONS
2847E V LIST OF TABLES
2.2-1 Recommended Data and Sample Acquisition - Hewlett-Packard 2.2-2 Arsenic Process Wastewater Data Summary 2.3-1 Trends in Properties of Elements of the Nitrogen Family 2.3-2 Toxic Effects of Arsenic 2.4-1 Summary of Arsenic Treatment Methods and Removals Achieved 2.4-2 Treatment Systems for Arsenic Removal 2.4-3 Pi lot Plant Arsenic Removal 2.4-4 Arsenic I11 - Sulfide Precipitation Reactions 2.4-5 Analysis of Actual Scrubber Blowdown Waters 2.4-6 Effect of Iron/Arsenic Ratio on Arsenic and Heavy Metal Separation 2.4-7 Analysis of Inlet Wastewater (Full Scale Plant) 2.4-8 Removal of Metals by Sulfide Precipitation and by Sulfide Precipitation Followed by Lime Precipitation (Full Scale Plant) 2.4-9 Comparison of Adsorption Capacity by Various Types of Powdered Activated Carbons 2.4-10 Comparison of Adsorption Capacity by Various Type of Granular Activated Carbon 2.5-1 Comparison of Potential Arsenic Treatment Processes
2847E vi LIST OF FIGURES
2.1-1 Sealed Quartz Ampoule GaAs Growth System 2.1-2 Liquid Encapsulated Czochralski (LEC Cz) Ingot Growth System 174 2.1-3 Gallium-Arsenide Ingot Crystals 2.1-4 Gallium-Arsenide Ingots and Wafers
2.2-1 Arsenic Wastewater Flow Diagram 2.2-2 Arsenic Production Rates 2.2-3 Percent Arsenic to HF Treatment System and Recycled Solids 2.2-4. Daily Liquid Flowrates
2.3-1 The Generalized Geochemical Cycles for Arsenic
2.4-1 Waste Reduc t ion Components 2.4-2 Mechanisms of Filtration 2.4-3 Beta Values in Use 2.4-4 Fi1 tration Equipment 2.4-5 Selection of Separation Process by Particle Size and Contamination Level 2.4.6 Sulfide Precipitation Plant (Boliden Metall, Sweden) 2.4.7 Effect of Ratio of Fe/As on Arsenic Removal by a Combination Hydroxide - Sulfide Precipitation
2.5-1 Selection of Separation Process by Particle Size and Contamination Level
2.6-1 Waste and Unit Classifications Used in California 2.6-2 Relationship Between Waste Classifications and Concentrations of Toxic Constituents
2847E Vii
b SUMMARY AND CONCLUSIONS
1. Arsenic contamination of HF Treatment process occurs almost entirely from overflow from the Gallium Arsenide (GaAs) Slurry Recovery process 1 iquid.
2. The sludge cake recovered from the HF Treatment System filter press is currently classified as Extremely Hazardous by Title 22 Section 66699 of the California Administration Code due only to its arsenic content.
3. An arsenic content reduction of 50 percent or greater in the overflow fluid from the GaAs Slurry Recovery system to the HF Treatment system will allow the sludge cake product to be reclassified as hazardous due only to its fluoride content.
4. Results of the Waste Extraction Test on the sludge cake material indicate arsenic is in an extremely inert and non-leachable form.
5. Hewlett-Packard's Gallium - Arsenide process is composed of many batch and semi-batch processes. The entire whole can also be considered a semi-batch process.
6. Waste reduction technology for removal of suspended arsenic solids from 1 iquid streams appears to be easi ly transferrable to other industries where heavy metal solids are involved.
7. Effective implementation of slurry recovery process filtration will not only eliminate arsenic-related hazardous wastes at Hewlett-Packard, but will increase the recyclable GaAs solids for sale to a recycle manufacturer.
9. The elimination of arsenic related hazardous wastes at Hewlett-Packard's San Jose facility will not require modifications of any of the steps currently necessary for GaAs microchip production.
10. The predominant form of arsenic in the GaAs microchip manufacturing process waste is paticulate GaAs.
viii 1.0 INTRODUCTION
Many electronic companies in the State of California process or manufacture gallium arsenide (GaAs) microchips, which creates a substantial volume of waste contalnfng arsenic. Generally, the concentration of arsenic in wastewaters or sludges exceeds sewer and municipal landfill limits for disposal, which-usually requires these waters to be treated and disposed to a Class I hazardous landfill. This practice is not only expensive, but undesi rabl e envi ronmental ly and economi cal ly as a long term mechani sm for waste di sposal .
This project has reviewed various processes to reduce, recycle and/or treat arsenic-laden wastes in a manner such that costs and disposal to the land are significantly reduced. The methods evaluated at various manufacturing stages included, but were not limited to, separation, precipi tation/ fixation, ion exchange, and arsine generation.
The information from this study is suitable for 1) design of a pilot or full scale treatment faci 11ty; and 2) widespread use within the electroni cs industry. Since the electronics industry is so large in California, particularly in Silicon Valley, the technological advances from this study should form the basis for other electronic businesses and facilities to reduce arsenic waste disposal to the land. Further, the treatment processes recommended by this study may be applicable to other industrial waste disposal problems involving arsenic.
The Hewlett-Packard Company (HP) currently operates a gallium arsenide (GaAs) microel ectroni cs chip manufacturi ng faci11 ty 1n San Jose, California. In the manufacturing process a solution of hydrofluoric acid is produced which contains significant levels of arsenic as well as non-hazardous constituents. The hydrofluoric acid solution is currently neutralized with lime which yields a calcium fluoride sludge containing high levels of arsenic. Other electronics companies utilize little or no treatment and haul the entire waste volume to a treatment storage and
2847E 1 disposal facility (tsdf). In 1985, HP produced 887,500 gallons of I I hydrofluoric acid wastewater and 25,219 gallons of calcium fluoride sludge.
The objective of thls project was to investigate processes to reduce substantially the amount of arsenic which Hewlett-Packard must dispose to the land. The results of this study have led to a proposed process to recycle or reclaim the arsenic from the wastes, hence eliminating land disposal of arseni c.
2847E 2 2.0 RESULTS AND DISCUSSION
(33) 2.1 DESCRIPTION OF GALLIUM ARSENIDE MICROCHIP MANUFACTURING PROCESS
The various manufacturing process steps which are described in the following pages are currently or potentially could be conducted at the Hewlett-Packard facility in San Jose.
Mi croel ectroni cs is a revolutionary technology which has expanded enormously in the last two decades, becoming of major economic and technological importance to the world. The development of semiconductor devices, first germanium and then silicon diodes, followed by the transistor and the integTated circuit, were the major factors in the evolution of micro- electroni cs. The use of gal 1 i"arsenide compounds have a1 so greatly contributed to the advancement of modern electronics.
The principal focus in recent years on a silicon alternative has concentrated on valence III/V compounds, such as gallium arsenide (GaAs), as a substrate material. As a semiconductor material, GaAs exhibits increased capabilities over silicon, such as electron mobility five to six times that of silicon. This characteristic, coupled with the semi-insulating substrate of GaAs, leads to increased performance in both speed and power consumption.
The technology involved in the growth of GaAs crystals is considerably more compl icated than that employed for si1 icon, and requires more preci se control in the ingot growth system. Two primary categories of 111-V semiconductor devices are -- Light-emitting diodes (LED) and microwave Intergrated Circuits (IC). LED's are fabricated from single-crystal GaAs which produce an mission band of red light. Green LEDs are generally composed of gallium phosphide (Gap).
Microwave IC devices are a specialized form of integrated circuit which is used as a high-frequency amp1 ifier for radar, telecommunications, telemetry, as well as octave and multi-octave amplifiers for use in electronic warfare systems . Microwave IC device manufacturers typi cal ly purchase the singl e- crystal GaAs substrates from outside vendors.
2847E 3 The following is a very brief discussion of the major steps required to form and manufacture GaAs microchips at Hewlett Packard's San Jose facility. This introduction to microchips processing will help in understanding the various arsenic sources that contribute to hazardous waste generation.
I Jnaot G row1ng
As in the silicon ingot and wafer growth process, elemental forms of gallium and arseni c, plus smal 1 quanti ties of dopant materi a1 -- si1 icon, telluri um or chromium -- are reacted at elevated temperatures to form ingots of doped singl e-crystal GaAs.
The bulk polycrystalline GaAs compound is normally formed by the reaction of As vapor wlth Ga metal at elevated temperatures in sealed quartz ampoules as shown in Figure 2.1-1.
One process gaining favor in to the commercial production of bulk single- crystal GaAs is shown in Figure 2.1-2. Here, the bulk GaAs is melted and the single crystal is slowly pulled out.
The singl e-crystal GaAs ingot must be sandblasted and cleaned to remove exterior oxides and contaminants. The resulting ingots appear as in Figure 2.1-3.
WAFER PROCESSING
Jnuot Cromi nq
The ends or tails of the single-crystal ingot are removed, as illustrated in Figure 2.1-4, using a water-lubricated single-bladed diamond saw, with various coolants added to the water.
2847E 4 FlGURE 2.1-1 SEALED QUARTZ AMPOULE GaAs GROWTH SYSTEM
RESISTANCE FURNACE
......
1 Atm 1260 OC
QUARTZ AMPOULE
1300 1
0 w 1100 U
U5 w n 900 5c
700 I 500 DISTANCE FIGURE 2.1-2 LIQUID ENCAPSULATED CZOCHRALSKI (LEC Cz) INGOT GROWTH SYSTEM 174
Incrl mosphere
Compound ,Seed Crystal Me’t \ \ Liquid B,03 cL \
0 0 0 0
0 0 0 0 0 0 FIGURE 2.7-3 GALLIUM-ARSENIDE INGOT CRYSTALS
FIGURE 2.1-4 GALLIUM-ARSENIDE INGOTS AND WAFERS Wafer Slicing
Gallium arsenide ingots are wax mounted to a graphite beam and sawed into individual wafers through the use of automatically operated inner diameter (ID) diamond blade saws. This operation is done wet with the use of lubricants and generates a gallium arsenide slurry, which is collected and recycled.
Wafers are wax mounted to the lapper using a hot plate, and are lapped on a machine exerting a set rotational speed and pressure. A lapping solution is fed onto the lapping surface and constitutes a slurry of aluminum oxide, glycerin and water. After a brief lapping period, the wafers are dismounted on a hot plate, rinsed in a soap solution and wiped dry.
Pol ishi nq
The wafers are then physically mounted to a mechanical polishing machine, using a sodium bicarbonate, 5% chlorine, water and colloidal sllica slurry.
EPITAXIAL GROWTH
The single-crystal GaAs wafers are used as substrates for the growth of very thin layers of the same or other 111-V compounds having the desired electronic or optical properties. Such crystal growth, in which the substrate determines the crystallinity and orientation of the grown layer, is called epitaxy, and a variety of epitaxial growth techniques are used in 111-V display and device production.
Reactor Load and Unload
The degreased and polished wafers initially receive a PRE-EPI etch and clean step. This involves a sequential wet chemical dipping operation utllizing surfuric acid, hydrogen peroxide and water; a de-ionized water rinse; and final ly, an isopropyl alcohol cleanldry.
2847E 5 The etch cycle is performed at the end of the growth cycle and on new quartz reactors to clean the interior surface of impurities.
Reacto r C1 eani nq
After each growth cycle, the reactors must be opened, the wafers removed, and the lower portion of the reactor physically cleaned. The lower quartz reactor and the bottom plate (base plate) are scraped clean using a metal tool, and the particulate material (mixture of GaAs, GaAsP, arsenic oxides and phosphorus oxides) is collected in a metal container positioned below the vertical reactor.
DEVICE FABRICATION
The GaAs wafer with an epitaxially grown layer of GaAsP on the upper surface proceeds into the device fabrication processing sequence.
Wet Etching
Various mixtures of wet chemical acid solutions are used in plastic baths in locally exhausted etch stations. The primary acids in use are sulfuric hydrofluoric, hydrochloric and phosphoric. As in silicon processing, hydrogen peroxide used with sulfuric acid and ammonium hydroxide (NH40H) provides a caustic etch.
Back1 aminq
Backlapping is done to remove deposited materials from the backside of the wafer. The wafers are wax mounted to a lapper plate and wet lapped with a colloidal silica slurry.
2847E 6 2.2 CHEMICAL CHARACTERIZATION OF WASTE STREAMS
In order to begin any waste reduction endeavor, a complete evaluation of the chemical process must be compl eted. Thi s evaluation requires the total cooperation of the faci 1i ty's management, operations supervi sors * operators and maintenance personnel. Hew1 ett Packard' s - San Jose faci 11ty management and staff have exemplified total cooperation in this evaluation and have made the arsenic waste elimination an easily achievable goal.
Identification of all possible sources of arsenic required education of the Envirosphere investigators by means of written 1i terature, lectures by Hewlett Packard's staff, and demonstrations and explanations by HP's process operating supervisors and staff. This education is one of the prime areas where HP demonstrated the kind of cooperation and know1 edge of their faci 11 ty and process that made the chemical characterization with respect to arsenic a rather comprehensive one.
Table 2.2-1 lists the process fluid samples and data required to be retrieved for each of the GaAs process steps thought to be contributing arsenic in HP's faciltty. Figure 2.2-1 illustrates how arsenic wastewater flows through that facility. Numbers listed here correspond to those on Table 2.2-1.
The first three arsenic sources were thought to be minor and composed of Soluble arsenic. These waste streams flow directly to the HF preholding tank and are not involved in the Slurry Recovery process. Sample acquisition for these sources required the operator to perform the wash process in a container with graduations on the sides for volume measurement. Samples were taken after the processes were completed. Arsenic analysis was done on the measured wash solution and with this analysis and the number of ingots or wafers cleaned or etched, a total arsenic contribution was calculated.
2847E 7 TABLE 2.2-1
RECOMMENDED DATA AND SAMPLE ACOUISITION - HEWLETT-PACKARD
1. Inaot C 1eani ng a. Obtain a 112 liter sample of the Aqua Regia (waste to HF system) solution plus rinse just before emptying contai ner.
b. Measure the volume of cleaning solution. c. Indicate how many ingots were cleaned in the solution sampled.
d. Indicate how many ingots are cleaned every month. e. Repeat steps a through c. f. Have the samples analyzed for arsenic. 2. W Etch a. Obtain a 1/2 liter sample each of the (waste to HF system) etch solutions.
b. Measure the volume of chemical the sample was taken from and indicate how many wafers have been etched. c. Indicate how many wafers are etched each month. d. Obtain a second sample the next day and analyze both for arsenic. 3. Furnace C 1eani ng a. Obtain a 112 liter sample of the cleaning (waste to HF system) solution. Catch the wash and first rinse solutions in a plastic container under the hood prior to sampling.
b. Measure the volume of solution the sample was taken from and indicate how many furnaces were washed.
c. Indicate how many furnaces are cleaned month 1y . d. Repeat the sampling a second day and analyze both for arsenic.
2847E 8 TABLE 2.2-1 (Continued)
RECOMMENDED DATA AND SAMPLE ACOUISITION - HEWLETT-PACKARD
4. Inaot Gri ndi ng a. Obtain records indicating the weight (waste to slurry system) of GaAs lost per ingot while grinding (coolant side) and the number of ingots ground per month. b. Obtain the liquid throughput of each grinding machine. 5. Inaot CroDDinq a. Obtain records that indicate the number (waste to slurry system) of cuts per ingot and the number of (coolant side) ingots per month.
b. Obtain throughput coolant volumes per croppi ng machi ne. 6. Wafer Slicing a. Obtain records indicating how many wafers (waste to slurry system) are sliced per month. This number, the (coolant side) width of the saw blade, and the ingot diameter will be used to calculate the GaAs sent to the slurry system per month.
b. Confirm that slicing machine uses about 100 gallday coolant and about 100 gallday of city water all of which flushes the GaAs into the slurry system. 7. Wafer Profilinq a. Obtain throughput rates for profiling (waste to slurry system) machines as well as average weight loss (coolant side) per wafer resulting from the profiling process. 8. LaDDinq a. Obtain records that indicate average (waste to slurry system) weight loss by thickness reduction and (non-cool ant side) by simple weight loss of wafers before and after 1appi ng . b. The throughput of liquid for each machine will be obtained as well as the length of time (hrs) each machine operates per month. 9. Chemi cal /Physical a. Weight loss per wafer will be estimated Pol ishi na from records based on thickness removed by - (waste to slurry system) pol ishi ng . (non-coolant side) 10. BacklapDinq a. Weight loss per wafer will be determined (waste to slurry system) for a least 20 wafers by weighing before (non-coolant side) and after back1appi ng . b. Obtain machine liquid flowrates. 2847E 9 TABLE 2.2-1 (Continued)
RECOMMENDED DATA AND SAMPLE ACOUISITION - HEWLETT-PACKARD
11. Coolant Side Circulating a. Obtain two 1/2 liter samples four (4) Liaui d hours apart. Analyze for arsenic, then filter through 0.45 micron paper and analyze arsenic in filtrate. Lab must calculate exact percent solids of each sample based on weight of GaAs on filter paper.
b. Have lab determine particle size distribution on each sample.
12. Non-Cool ant Side a. Obtain two 1/2 liter samples four (4) circul atina Liauid hours apart. Analyze for arsenic, then filter through 0.45 micron paper and analyze arsenic in filtrate. Lab must calculate exact percent solids of each sample based on weight of GaAs on filter paper.
b. Have lab determine particle size distribution on each sample.
13. S1 irry System a. Obtain four 112 liter samples four (4) Overflow to HF Svstem hours apart. Analyze for arsenic, then filter through 0.45 micron paper and analyze arsenic in filtrate. Lab must calculate exact percent solids of each sample based on weight of GaAs on filter paper.
b. Measure the liquid flowrate until reason- ably comparable rates are obtained.
14. Preholding Tank to a. Obtain two 112 liter samples four (4) Hol di na Tank Flowrate hours apart. Analyze for arsenic, then filter through 0.45 micron paper and analyze arsenic in filtrate. Lab must calculate exact percent solids of each sample based on weight of GaAs on filter paper.
b. Measure the liquid flowrate until reasonably comparable rates are obtained.
C. Measure flowrate on two(2) separate days.
d. Obtain preholding tank volume.
2847E 10 TABLE 2.2-1 (Continued)
RECOMMENDED DATA AND SAMPLE ACOUISITION - HEWLETT-PACKARD
15. Holding Tank OutDu t a. Obtain two 1/2 liter samples four (4) hours apart. Analyze for arsenic, then filter through 0.45 micron paper and analyze arsenic in filtrate. Lab must calculate exact percent solids of each sample based on weight of GaAs on filter paper.
b. Measure the liquid flowrate until reasonably comparable rates are obtained.
C. Measure flowrate on two(2) separate days.
d. Obtain holdi ng tank volume.
16. Coolant Side Inlet a. Obtain two 1/2 liter samples two(2) hours F1 uid apart.
b. Have lab analyze partial size distribution on each sample.
17. Non-Coolant Side a. Obtain two 1/2 liter samples two(2) hours Inlet Fluid apart.
b. Have lab analyze partial size distribution on each sample. 18. HF System Sludae Cake a. Obtain two(2) representative samples. b. Have EPA 1i sted metal s determined.
C. Have the lab run the NET test on each sample as per Title 22 of California Administrative Code.
2 847 E 11 FIGURE 2.2-1 GALLIUM-ARSENIDE MICROCHIP MANUFACTURING ARSENIC WASTEWATER FLOW DIAGRAM
WETETCHING 2
RECYCLE 11 HF PRE BUILDING 90
WASHWATER . IVERFLOW t+'bl INGOTCROPPING 5 1-b COOLANT '0HF SIDE iYSTEM SLURRY +4 I 4 + WAFERSLICING 6 I RECOVERY 3 HF HOLDING HF HOLDING I , '6 WAFERPROFILING 7 I 00 RECYCLE 12 I I LAPPING NON-COOLANT 'iL+ 18 CHEMICAU I HFTREATMENT SLUDGE CAKE. PHYSICAL POLISHING SLURRY + SYSTEM FROM RECOVERY FILTER PRESS BACK LAPPING 1 o 20 I T DRIED GaAs NEUTRALlZATlON ACID WASTE STREAM 1 g SYSTEM TO SEWER SYSTEM 21 BUILDING 90 & 91 Obtaining data for streams 4 through 10 involved acquisition of detailed and confidential company records that listed the average number of GaAs ingots produced per month, the average number of wafers cut from each ingot, the exact weight loss for each cropping and grinding operation, and the exact dimension change and weight loss per wafer for each manufacturing operation. Since these operations requl re exacting procedures and are batch type processes, it was concluded that weight loss records would provide data far superior to that obtained from liquid sampling and liquid rate measurements. Because of this decision and the fact that some of this machinery uses recycled as well as fresh water, no liquid measurements were made on streams 6 through 10.
Laboratory analysis samples taken on streams 11 and 12 were to be used to evaluate the currently active GaAs Slurry Recovery process and to provide particle distribution data for any sol ids recovery process (fi1 tration) to be recommended. Flow measurements were not possible because stream 12 was not in use (no recycle) during the study period, and stream 11 recycle (although in operation) does not contribute any data toward evaluation of arsenic sources. Extensive flowrate data will be necessary only when solids recovery equipment specification and design (Step I1 Grant) are in progress.
Evaluation of wastestream 13 involved sampling the intake of a concrete sump pump which was equipped with a float-activated switch. Sampling was easily performed with flow rate measurement being taken from the average number of pump cycles per month and the cycle volume. Observations of pump cycle times along with the calculated flowrate confirm that this flowrate is indeed very small.
Flow measurements and laboratory samples for streams 14 and 15 were easily obtained by HP personnel. Measurements confirm that the HF and washwater contributes almost all of the 5,000 gallon per day flowrate to the HF Treatment system. Analysis of the HF and washwater for arsenic indicate that none is present in detectable amounts.
2847E 12 Measurements of streams 16 and 17 were made for the same reasons as streams 11 and 12. That is, for evaluation of particle size distribution and slurry recovery process evaluation. It was found that inlet fluid composition was highly dependent on which wafer manufacturing operations were being performed at the time. This obstacle led, in part, to the decision to use GaAs weight loss data on file rather than base the evaluation on such non-steady state sampling data.
Chemical analysis of the HF Treatment System Sludge Cake (#la) indicates that this material is considered to be extremely hazardous solely because of its arsenic content. Waste Extraction Tests (WET) indicate that this arsenic is in an extremely inert form and that even in its elevated concentration it produces a WET test result with a non-hazardous leachate. Our conclusion is that a 50 percent reduction in arsenic content in the sludge cake would produce a solid material classified as non-hazardous by the State of California except for fluoride content. This would result in total arsenic waste elimination at Hewlett-Packard's San Jose facility.
Arsenic analysis of the other waste streams at HP's facility completed our chemical characterization. Results are listed in Table 2.2-2 and illustrated in Figures 2.2-2, 2.2-3 and 2.2-4. Figure 2.2-2 indicates the sources and amounts of the average monthly arsenic weights that are produced at HP's San Jose facility (Table 2.2-2 data column 2). The most important point here is that nearly all (about 94%) of the arsenic that flows to the HF Treatment System is from the Slurry Recovery process and is essentially all solid GaAs particles. The remainder is entirely soluble arsenic from the cleaning and etching processes.
Figure 2.2-3 presents information tabulated in Table 2.2-2 (data column three) and illustrates the relative amounts of arsenic produced from each source with respect to GaAs solids currently recycled off site and arsenic disposed of as a hazardous waste in the sludge cake from the HF Treatment system. Daily liquid flowrates are indicated on Figure 2.2-4 and in Table 2.2-2. Here, the most important conclusion to be drawn is that a
2847E 13 TABLE 7.2-2 ARSENIC PROCESS WASTEWATER DATA SuMF4MV
Percent Arsenic to HF Treatment Total Arsenic Soluble Arsenic Stream Liquid Flowrate Arsenic Rate System and Concentration Concentration Number Stream Source (GPD) ( 1 b/MO Recycled Solids (l?@L) Percent Solids (mg/L 1
1. Ingot Cleaning 0.6 0.03 0.04 <0.1 2. Wet Etching 0.66 0.93 c0.1 3. Furnace Cleaning <0.1 0.02 0.03 0.0 Ib/mo HF i3 WASHWATER 23 0.03 lblmo INGOT CLEANING 1 0.71 lblmo 0.66 lblmo WETETCHING 2 0.02 Ib/mo RECYCLE 11 51.43 Ib/mo BUILDING 90 I WASHWATER 1.43 lWmo OVERFLOW INGOT CROPPING 5 COOLANT SIDE SLURRY 14 f f WAFER SLICING 6 11.81 lblmo RECOVERY 3 BUILDING BUILDING 0.60 lWmo 41 WAFER PROFILING 7 HF HOLDING UF HOLDING RECYCLE 12 bI LAPPING 8 1 I I NON-COOLANT CHEMICAU SIDE 9 HFTREATMEM PHYSICAL POLISHING SLURRY + SYSTEM RECOVERY 3.70 lWmo FILTER PRESS 20 BACKLAP-1 17 41 , 58.88 Iblmo 0.95 Ib/mo I NEUTRALIZATION 1-b ACID WASTE STREAM 1.18lb/mo 19 SYSTEM TO SEWER- SYSTEM 21 BUILDING 90 & 91 _m_- - FIGURE 2.2-3 GALLIUM-ARSENIDE MICROCHIP MANUFACTURING ARSENIC WASTE WATER FLOW DIAGRAM PERCENT ARSENIC TO HF TREATMENT SYSTEM AND RECYCLED SOLIDS - 0.0% HF & WASHWATER 23 0.04% INGOTCLEANING 1 r 1 .OO& I I RECYCLE 11 HF PRE BUILDING 90 72.76% I HF AND 15.69% WASHWATER 2.02% NERFLOW INGOT CROPPING 5 COOLANT -0HF SIDE iYSTEM SLURRY 14 16.71 Yo RECOVERY 3 + c BUILDING BUILDING 0.84% 16 WAFER PROFILING 7 HF HOLDING HF HOLDING RECYCLE 12 1.09% -r 16.69”/0 LAPPING -1 8 I 1 I I I HFTREATMENT SYSTEM FILTER PRESS BACKLAPPING io I 83.31% DRIED GaAs SOLIDS NEUTRALIZATION ACID WASTE STREAM 19 SYSTEM TO SEWER SYSTEM 21 BUILDING 90 8 91 I FIGURE 2.2-4 GAL LIUM-A RSENIDE MICROCHIP MANUFACTURING ARSENIC WASTE WATER FLOW DIAGRAM DAIL Y LIQUID FLO WRA TES - HF & WASHWATER 23 0.6 GPD INGOTCLEANING 1 RECYCLE 11 166 GPD 1 BUILDING 90 INGOT GRINDING 4 HF AND WASHWATER 7.8GPD 10.2 GPD IVERFLOW COOLANT '0 HF SIDE ;YSTEM SLURRY RECOVERY I3 BUILDING BUILDING I6 WAFER PROFILING 7 HF HOLDING HF HOLDING I RECYCLE 12 TANK 22 10,000 GPD NON-COOLANT 18 CHEMICAL/ 9 SIDE PHYSICAL POLISHING SLURRY -1111) HFTREATMENT SLUDGE CAKE SYSTEM RECOVERY FROM FILTER PRESS 17 I 170,000 GPD NEUTRALIZATION ACID WASTE STREAM 19.- SYSTEM TO SEWER- SYSTEM 21 BUILDING 90 8.91 155,000 GPD waste stream with a flowrate of approximately eight (8) gallons per day of GaAs-laden liquid overflowing to the HF Treatment System is responsible for about 94 percent of the arsenic in the sludge cake solids. Considerations of other wastewater streams such as the Building 90 HF and Washwater and the Acid Waste stream were made but either the arsenic content was confirmed by analysis to be below detection limits or it did not fall within the scope of this investigation. In either case, the levels are very low and do not present a potential arsenic contamination source. In fact, the wastewater treatment systems in place at HP's San Jose facility produce a wastewater stream to the sewer system at least 20 times lower than this discharge permit allows. In summary, arsenic solids (GaAs) represent at least 94% of the arsenic contam'ination found in the sludge cake produced from the HF Treatment process. These sol ids are produced from physical sawing, grinding and polishing operations and are present in the overflow liquid from the Slurry Recovery process. Removal of these solids from this water flowing to the HF Treatment process by a filtration technique appears to be the most direct and simple process from a chemical engineering point of view. Although filtration is possible, a review of other arsenic removal processes is important. In order to choose the best system for arsenic recovery, a working knowl edge of arsenic chemi stry is requi red. Thi s knowl edge, along with information regarding potential arsenic removal processes, should be considered before correct engineering design of the wastewater treatment system can be initiated. Detailed discussions of both areas follow. 2847E 15 2.3 ARSENIC CHEMISTRY Arsenic is a member of the nitrogen family of chemical elements which is composed of Nitrogen (N), Phosphorous (PI, Arsenic (As), Antimony (Sb) and Bismuth (Bi). Each of these elements has five valence electrons per atom. There is a tendency in these elements to take up electrons from the more metallic elements for form triply charged negative ions. Nitrogen forms nitride ion, N---, on reaction with certain active metals, and phosphorous somewhat less readily forms phosphide ion, but the other members of the group show little or no inclination in this direction. This is in accord with the general tendency for the elements of a family to become more metallic with increasing atomic number. This same trend is reflected in the order of decreasing ionization potentials and decreasing relative electronegativities ---N > P > As > Sb > Bi. (1 1 The elements of the nitrogen family form hydrides of the general formula MH3. They also form oxides in which the element is in the +3 or +5 oxidation state. The physical properties of the free elements show a regular graduation from nonmetallic to metallic with increasing atomic number. Like the first members of other families, nitrogen differs in many respects from the other members of its family. (1) Some of the general trends in the nitrogen family are summarized in Table 2.3-1. Arsenic and antimony occur more widely, though in lower total abundance, and are often associated with sulfide minerals, particularly those of Copper, Lead and Gold. 2.3.1 ELEMENTAL ARSENIC The normal form of As, is bright and metallic in appearance and has crystal structure similar to that of black Phosphorous. The metal burns in air 2847E 16 TABLE 2.3-1 TRENDS IN PROPERTIES OF THE ELEMENTS OF THE NITROGEN FAMILY PH3 AsH3 SbH3 BiH3 NH3 Decrease in Basic Character - Decrease in Stability N2°3 '4'6 As 4'6 Sb406 Bi203 Aci dic Decrease in Acidic Character Sb4010 Bi206 N2°5 '4'1 0 As401 0 Strongly Acidic Weakly Aci dic Decrease in Acidic Character NC1 PC1 AsCl SbCl BiC1 Increase in Ionic Character -- Decrease in Ionization Potential 2847E 17 on heating to form the oxide, and it reacts directly and readily with halogens and some other nonmetals. Dilute non-oxidizing acids are without effect on it, but with strong acids such as nitric acid, arsenic acid is produced (2) . Arsenic combines readily with many nonmetals and also reacts with many metals to form compounds called arsenides. In moist air, arsenic oxidizes to form arsenic trioxide (As406). 2.3.2 COMPOUNDS OF ARSENIC The trioxide, As406 is the common oxide of arsenic. AS4010 is a white solid that decomposes with heat into the trioxide and oxygen. Arsenic forms two series of acids, the arsenious and arsenic acids, which are somewhat similar to the acids of phosphorus. A water solution of As406 is called arsenious acid; the oxide, however, Is not very soluble. Arsenic acid, H3As04, is prepared by the oxidation of As406 with nitric acid (3) . As406 + 4 HN03 + 4 H20 * 4 H3As04 + 2 N203 t The two halides that are formed by arsenic, AsC13 and AsF5, hydrolize 1ess readi ly than the corresponding ha1 ides of phosphorus. Three sulfur compounds of arsenic have been discovered, but they are not important commerically. They are arsenic disulfide, As2S2, arsenic trisulfide, As2S3 and arsenic pentasulfide, As2S5. They can be prepared by heating a mixture of arsenic and sulfur in the calculated amounts. Arsenic trisulfide is a yellow crystalline solid that can be precipitated from solution by H2S. 2 H3As03 + 3 H2S * 6 H20 + As2S3 1 2847E 18 The pentasulfide, As2S5, a yellow solid, can be precipitated from a solution of arsenic acid by H2S. 2 H3As04 + 5 H2S 8 H20 + As2S5 1 Arsenic forms thio acids and their corresponding salts. Soluble sulfides such as Na2S and (HN4I2S are used in chemical analysis to dissolve the sulfides of arsenic and thus separate them from a mixture of metal sulfides (3) 3 Na2S + As2S3 - 2 Na3AsS3 } soluble 3 Na2S + As2S3 -. 2 Na3AsS4 } soluble The in'soluble metal sulfides are separated by filtration and the arsenic sulfides are recovered by treating the filtrate with HCl(3). 2 Na3AsS3 + 6 HC1 - 6 NaCl + As2S3 1 + 3 H2S t Arsine, AsH3, is formed by the action of hydrogen on compounds of arsenic. 12 H2 + As406 -. 6 H20 + 4 AsH3 t Arsine has a garliclike odor and, like all arsenic compounds, is extremely poisonous. The gas burns in oxygen and forms the trioxide and water. 4 AsH3 + 6 O2 -. 6 H20 + As406 At high temperatures, arsine decomposes into its elements. 4 AsH3 7 H2 t + Asq The hydrogen compounds of arsenic, corresponding to the general formula MH3,-have electronic and geometric structures analogous to those of ammonia and phosphine. 19 Arsine is definitely poisonous, even in small amounts (1) . Arsine like the others in this group is prepared by either the hydrolysis of metal 1i c arsenides Na3As + 3H20 = 3Na' + 30H- + AsH3 or by the reduction, by active metals in acid solution, of compounds of arsenic in the higher oxidation states. When, for example, a solution of a sol ubl e arseni te in di 1Ute sul furic acid is treated wi th metal 1i c zinc , arsine gas is produced and is evolved along with the hydrogen formed by reaction of the zinc with the acid (1 1. As03 + 9H+ + 3Zn = ASH~+ 3Zn++ + 3H20 The reaction just described, along with the relatively easy thermal decomposition of arsine, constitutes the basis for an exceptionally sensitive test for arsenic, known as the Marsh test. A solution of the substance to be tested is introduced into a flask containing zinc (or some other active metal) and an acid. If arsenic is present, arsine gas is produced. If the arsine gas is heated, it decomposes to give a shiny black mirror-1 ike deposit of elemental arsenic (1 1 . Arsenic forms both +3 and +5 sulfides with the formulas As2S3 and As2S5, respectively. These are usually obtained by precipitation with hydrogen sulfide according to the fol lowing equations. 2H3As04 + 5H2S = As2S5 1 + 8H20 2SbC13 + 3H2S = Sb2S3 1 + 6H+ + 6C1- 2847E 20 The arsenic sulfides are yellow in color and are soluble in concentrated acids. The sulfides, like the oxides, are soluble in basic solutions, but of particular interest is their ready solubility in solutions of sulfides or hydrosulfides to yield the thioarsenites Ass3 and Ass4. These reactions are used in many qualitative analytical procedures for the separation of the sulfides of arsenic from the sulfides of mercury, lead, copper, bismuth, and cadmium. Arsenic also forms a sulfide having the molecular formula As4S4, which provides an interesting example of the fact that the molecular formula of a compound does not necessarily provide any indication as to the valences of the atoms involved(1 1 . 2.3.3 a PHYSICAL - CHEMICAL ASPECTS Compounds of arsenic in various chemical forms have most prominently figured in the extensive history of the toxicology of the element. Geochemically, arsenic is encountered as a component of sulfidic ores, occurring as the arsenides and diarsenides of metals such as nickel, cobalt, and copper, and is present in rocks and soils at trace levels. Smelting of commercially important metal ores, therefore, often has associated with it the release into the environment of significant quantities of certain arsenic compounds. For example, arsenic trioxide, As203, a major form of the element in terms of its toxicological history, is a smelter product arising from air roasting of metallic arsenides or arsenic-containing sulfides (25) . Arsenic trioxide, white arsenic, is only slightly soluble in water and other solvents which do not promote chemical transformation. Its solubility in solvents which mimic physiological media may not necessarily be the same as for simple solvents, e.g., gastric juice versus water. Arsenic trioxide sublimes, the process becoming pronounced at 135'C. This property appears to have been overlooked through the years in considering analytical methods for measuring levels of the compound. Dissolution of the trioxide in aqueous media leads to formation of arsenous acid, H3As03, while alkaline treatment eads to formation of the arsenite ion, AsO(OH);, 2847E 21 with both the acid and the salt being freely soluble in a number of solvents(25) Arsenic pentoxide, As205, may be readily prepared by nitric acid oxidation of elemental arsenic or the trioxide. Compared to the trioxide, the pentoxide has considerable solubility in water (63.0 g/100 g water), presumably dissolving to form the relatively strong arsenic acid H3As04 (25) . The relative stability of solutions of arsenfc or arsenous acids to oxidation-reduction is of considerable importance in terms of valency- dependent arsenic toxicity. In oxygenated media, one would expect the pentavalent form to dominate, while reducing media would favor the trivalent state(25). Arsenous and arsenic acids both form mono-, di- and tri-metal salts, the a1 kal I-metal salts such as potassi urn and sodium arsenite bel ng freely sol ubl e in water and the alkaline salts such as calcium or magnesium arsenite being slightly soluble(25) . While tri-organic esters of the tri- and pentavalent arsenic acids are known, they are labile to hydrolysis and one would expect the mono- and di-organic derivatives to be even more so. This behavior has fmplications In the postulated role of arsenate ions in interfering with phosphorylation reactions(25) . Arsine (arsenic ttihydrlde, AsH3) is a strong hemolytic toxicant and probably the most poisonous of the arsenicals. Although generally a minor factor in the environmental chemistry of arsenicals, it can form under certain restricted conditions, i.e., via reduction in the presence of an active hydrogen-generating source (25) . Monomethyl and dimethyl arsenic, in the form of methylarsonous and methyl arson-ic, dimethylarsinous and dimethylarsinic (cacodylic) acids, occur both in the environment and are formed via in vivo transformation in many mammalian species, including man. Such organic arsenic compounds are also of commercial significance. For instance, both methylarsonic and 2847E 22 dimethylarsinic acids, usually in the form of the mono- or dialkali salts,are employed as herbicides which, when released into the environment, may undergo reduction to the corresponding labile arsine compounds, CH3AsH2 (methylarsine) and (CH3)2 ASH (dimethylarsine). Like trivalent inorganic arsenic, methylarsonous acid can interact with thiol groups (as can cacodylic acid) to form the CH3-As(-S-I2 and (CH3I2-As-S groups , respectively. The physical forms of arsenic in the environment depend on its mode of emission and subsequent interactions with other mater! a1 s (25) Arsenic, along with other trace metals, can be mobilized in association with airborne particles derived from high-temperature sources such as fossi 1- fueled power plants, metallurgical smelters and blast furnaces (25) . Arseni c compounds form insol ubl e compl exes with sol 1s and sediments. With soi 1s , the interacti on invol ves clay surfaces contai ning amorphous alumlnimum or iron oxides (25) . 2.3.4 ENVIRONMENTAL CYCLING OF ARSENIC Inorganic arsenic is released into the environment from a number of anthropogenic sources which include primary copper, zinc and lead smelters, glass manufacturers (specifically those that add arsenic to the raw materials) and arsenic chemical manufacturers. Figure 2.3-1 presents a general ized scheme for the geochemical cycling of arsenic through various compartments of the environment. The atmosphere is a major conduit for arsenic emitted from anthropogenic sources to the balance of the cycle via wet and dry precipitation processes. The rate of movement of arsenic from the atmosphere is not known at present(25) . Dry and wet fall onto soils may be followed by movement through soils either into ground water or surface water. Passage of arsenic into surface waters may then be followed by further transfer to sediments (25) . Compli cat1ng an understanding of the envi ronmental cycli ng of arsenic is the ex! stence of chemical and biochemical transformations which occur within the cycle(25) . 2847E 23 FIGURE 2.3- 1 THE GENERALIZED GEOCHEMICAL CYCLES FOR ARSENIC (25) INHALATION OF DUST BIOSPHERE DEGRADATION ,rrrrr IIIIIIIIIIIII I AND ~ASEOUSFORMS PLANTS------ANIMALS I ARSENIC 4 OF I t I I DEGRADATION t SOLUTIO'B\SEIONAN ABSORBTIO I I I I I A ATMOSPHERE PHtGIPI I A I IWN I I I A 1 CHEMICAL PREClPlTATlO AND SEDIMENTATIO MECHANICAL OF SOLID WEATHERING SOLUTION ANI: MECHANlCAl IWEATHERlNC *rrrrrrrrrrrrrrrrDUST I I LITHOSPHERE I I ROCKS ARSENIC-BEARING I CHEMICAL PRECIPITATION DEPOSITS PRECIPITATION AND CONSOLIDATION OF SOLIDS Trival ent arseni c in the atmosphere can undergo 0x1dation to the pentaval ent state. Such conversion can also occur in aerated surface waters. On the other hand, pentavalent arsenic in an aqueous medium which is somewhat acidic is an oxidant, and, in the presence of oxidizable material, it will (25) react to form trivalent arsenic . Reduction and methylation of inorganic arsenic occur only to a limited extent in soils, 1-2 percent over a period of months having been reported in one study(25). In terms of the relative amounts of arsenic partitioned among the various envi ronmental compartments, Suta (1 980) has calculated that 1and is the major sink for arsenic, accounting for approximately 90 percent of the dissipation for the year 1974. The atmosphere accounts for 7-8 percent dissipation with the least quantity appearing in waterborne effluents(25) . 2.3.5 HEALTH EFFECTS OF ARSENIC AND COMPOUNDS Arsenic, may present a health hazard to humans when it is released into the environment as a consequence of industrial processes. The preponderance of cli ni cal and epidemiological evidence regarding the effects of arsenic pertains to trivalent inorganic arsenic. Much of this evidence suggests that trivalent inorganic arsenic is a carcinogen. Some limited evidence suggests that pentavalent inorganic arsenic may also be carcinogenic. The main routes by which arsenic enters the human body are inhalation and ingestion. Experimental studies show that following injection of trivalent inorgani c arseni c, arseni c is concentrated ini ti a1 ly in the 11ver, kidneys, lungs, and spleen. After 24 hours the level in the liver and kidneys decreases, while that in the skin increases. Both tri Val ent and pentavalent arsenic are mutagenic and teratogenic in animal tests. Attempts to induce tumors in experimental animals by arsenic usually have been unsuccessful, although, significantly in some instances, positive results have been obtained. Animal toxicity studies indicate that tri Val ent arsenic is several times more toxic than pentavalent arsenic. 2847E 24 Epidemiological studies of smelter workers show excess lung cancer risk in individual s exposed to arseni c trioxide, and several studi es indi cate that the risk increases with increasing duration and level of exposure. Risk increases of up to 8-fold have been reported. It is possible that the increased risk is not due to arsenic alone, since smelter workers are exposed concomitantly to sulfur dioxide and other toxic substances. Workers engaged in the manufacture of arsenical pesticides also showed elevated risk for pulmonary cancer. Such workers, though not exposed to sulfur dioxide, may be exposed to other toxic substances. Similar results have been recorded in vineyard workers in France and Germany, where the workers were exposed to pesticides containing trivalent and pentavalent arsenic. In the United States, agricultural workers exposed to lead arsenate spray (pentavalent) evidenced excess lung cancer associated with this process. The cirrently avai lable experimental and epidemiological evidence does not provide an adequate basis for gauging the effects of chronic low-level exposure to arsenic compounds. A clear dose-response effect has been noted in a large-scale study in which ingestion of drinking water containing arsenic was associated with subsequent development of skin cancer. It is reasonable to assume that smaller dosages of inhaled arsenic could be involved with the development of cancer, since inhalation is a more efficient route of entry to the body than ingestion. In addition, as noted above, dose-response relationships have been reported in smelter workers. Toxic effects of arsenic on humans through ingestion, injection and inhalation are furnished in Table 2.3-2. It is difficult to determine a specific level of exposure associated with a specific level of risk because the precision of ambient air measurements is low; the level may be incorrect by as much as one order of magnitude. Nevertheless, the air levels yielding standard mortality ratios of 800 (i.e., an 8-fold increase in lung cancer deaths) have been estimated at 23 to 323 pg of arsenic per cubic meter of air. American Conference of Government-Industrial Hygienists I~c.~have determined a threshold limit (TLV) of 0.2 mg per cubic meter of air. The toxic effects of arsenic on humans is shown on Table 2.3-2. 2847E 25 TABLE 2.3-2 TOXIC EFFECTS OF ARSENIC a compound Route of entry Acute offectm Trivalont inorqania Ingemtion Throat conmtriction, dlffioulty mwallwing, violent armenia abdomina1 pin, vomiting, mumcular cramp, pomaiblo death vlthin 1-4 day. ?atty infiltration of aellm (empeclally livor cel1m)t direct toxia actlon on cardiac wmclet ECO abnormal- itlea 1V injoation Storutitim, albuminuria, jaundico, blood dymcraaiae, dernrstitia, movere cerebral mymptoam, acute hepatitle, ascitem fnhala tion Enlargenant of tho liver, hmoglobinuria, jaundice, hemolytic anemia, abdominal pln, vomitingr acute uremia io a conunon cause of death (from 4th day onvards)t fatty degeneration of cells, particularly those of the liver, kidneys, and cardiac musculature Chronic effects Inorganic armenic Ingeetion Naumea, vomiting, conjunctivitim and catarrhal state of expomed mucous membranes of the nose, larynx and respiratory pamsages, keratoaea. nclanomia Inhalation Perforation of the nasal meptumt Rtinnskir Disease (chronic 'rhino-pharyngo-trachm-bronchitis") hepatitim, jaundice, peripheral neuritis l Source: Buchanan (1962). Arsenic compounds such as the arsen tes are important herbicides, calcium and other arsenates are insecticides; sulfides are pigments, rodenticides and used in pyrotechnics; gallium arsenide Is in semiconductors; arsenic trichloride is employed in chemical synthesis; the gaseous tri- and pentafluorides apparently have no important commerical uses. Many organic arsenic compounds, however, have been employed in medicine, or as war gases (4) . As with other metallic poisons, the toxicities, especially the acute toxicities, of arsenic compounds are related to their solubility in water. Thus most arsenates and arsenites are acute poisons, while the sulfides are probably less toxic in an acute sense, but may be equally hazardous on prolonged exposure. Elemental arsenic is also less acutely toxic than its oxides, except for the rare yellow arsenic which is highly toxic, possibly similir to yellow phosphorus in some of its properties(4) . Systemic arsenic poisoning is rarely seen in industry, and still more rarely is it severe in character. It is hard to explain the difference between industrial and nonindustrial arsenic poisoning, but such variation is recorded in all industrialized countries. The usual effects on workers are local, on skin and mucous membranes, etc. A hoarse voice is characteristic of an arsenic worker, and a perforated nasal septum is a common result of prolonged inhalation of white arsenic dust or fume. A few documented cased of cirrhosis of the liver, however, due to occupational exposure to arsenic, have been recorded(4) . Although the epidemiologic evidence is not complete, arsenic is considered by some to be a carcinogen, certainly of the skin, and perhaps of the bronchi. Cancers from exposure to arsenic have followed: 1) the internal use of Fowler's Solution, an aromatic solution of potassium arsenite; 2) inhalation and skin contact with sheep-dust, a mixture of sodium arsenite and sulfur; 3) the combined inhalation of As203, SO2 and other particulates from the smelting of ores containing arsenic. Experimental cancers in animals have not been produced from As203 despite several attempts and the conclusion of Vallee, et al. was that "it is improbable 2847E 27 that arsenic (per se) plays a significant role in the generation of cancer." The belief that other occupational factors are necessary for the development of cancer, in addition to arsenic exposure, has been expressed by others (4) . A search of the world literature reveals no reports of industrial or experimental exposures solely to arsenic compounds whi ch contain both environmental and toxicological criteria from which a TLV can be unequivocally based. Watrous and McCaughey found concentrations of arsenic 3 in a pharmaceutical plant averageing about 0.2 mg/m , with no definite evidence of intoxication. Pinto and McGill studied a group of smelter employees and found an average urinary arsenic excretion of 0.8 mg/L. The chief manifestation of toxic exposure was dermatitis, with perforation of the nasal septum, pharyngitis and conjunctivitis noted less frequently. A reasonable interpretation of the urinary arsenic 1eve1 s would indicate an 3 average exposure of about 0.2 mg/m of arsenic in air. Since individual concentrations as high as 4 mg/L of urine were found, it is probable that many workers were exposed at higher concentrations (4) . In its criteria document for inorganic arsenic, NIOSH in 1973 recommended 0.05 mg As/m 3 (as a TWA) as a workplace air standard. This was changed in 1975 to 0.002 mg/m3 as a 15 minute ceiling(4). The first limit was based primarily on reports of cancer among workers exposed to arsenic, as we1 1 as non-occupational cancer resulting from arsenic medications. The only pertinent environmental data cited not already noted consist of an average concentration of 0.56 mg/m 3 computed from the paper from Perry et a1 on an English sheep dip factory study, and a study by Lee and Fraumeni in a smelting plant. Concentrations of 1.47, 1.50 mg/m 3 were reported in "medium and high exposure area" and 0.65, 0.17 and 0.002 mg/m3 in "light exposure areas". In both plants an increased incidence of cancer was reportedly found (4) . There appears to be no published explanation of the reasons for the reduction of the NIOSH 1973 recommendation of a TWA of 0.05 mg/m3 as a standard, to a ceiling of 0.002 mg/m3 in 1975(4). 2847E 28 Normal values of arsenic in urine, as recorded in the literature, vary from 0.013 to 0.046 mg/L, to 0.13, to 0.025 mg/L. The urinary excretion, in mglliter, of elements that are freely eliminated by this route, such as fluorine, mercury and arsenic, is at most 2.5 to 5 times the occupational exposure in mglcubic meter of air. It is apparent that biological monitoring for arsenic by urinalysis would be of limited value in determining whether or not the NIOSH recommended standard was being met or exceeded (4) . According to the 1977 compilation of occupational exposure limits of the International Labour Office, the following countries had adopted the 3 previous TLV of 0.5 mg/m : Australia, Finland, Japan, Holland, Switzerland and Yugoslavia. Czechoslovakia, East Germany, Hungary and Poland specified the USSR MAC of 0.3 mg/m3; Romania 0.2 and Sweden 0.05 mg/m3: Only three of 18 countries (West Germany, Italy and Sweden) designated arsenic and compounds as carcinogens, a1 though Belgium and the Nether1ands so characterized arsenic trioxide (4) . It is possible that some arsenic compounds, the trichloride for example, might produce certain toxic effects at concentrations below 0.2 mg/m 3 of arsenic. Data to substantiate this speculation are lacking. The contrary situation, that some compounds, or the metal itself, are chronically less toxic than As203, the form for which most information is available, seems more probable in the light of present knowledge. Therefore, a TLV of 0.2 mg As/M 3 for soluble compounds of arsenic is re~ommended'~). 29 2.4 IDENTIFICATION OF POTENTIAL TREATMENT PROCESSES 2.4.1 INTRODUCTION The primary goal in hazardous waste reduction in a chemical process facility is to accomplish the task without impacting the process itself and to, if possible, generate a saleable product that has been generated from the waste redu c t ion 'I treatmen t I' . Figure 2.4-1 illustrates the components involved in any consideration of waste reduction. It was the goal of this grant to identify a treatment process or processes that could be easily applied to arsenic waste reduction in the Gallium-Arsenide microchip manufacturing process. As stated above, that goal has been achieved. 2.4.2 GENERAL DISCUSSION Arsenic and arsenical compounds have been reported as waste products of the metal 1 urgi cal industry, glassware and cerami c production, tannery operations, dye, and pesticide manufacturer. Other industrial sources include the organic and inorganic chemical s and petroleum refining industries, and the rare-earth industry. The manufacture of Pari s green and calcium meta-arsenate, both insecticides, was reported to produce wastewaters contai ni ng arsenic(5). A1 though arsenic is widely associated with the manufacture of herbicides and pesticides, a recent study concluded that the inorganic pesticides industry (including arsenic based compounds) is fading(6). Arsenical wastes from these sources would be expected to assume less importance in that event. Arsenic wastes from nonferrous smelting have been reported in the litera- ture, although the main form appears to be as extremely small particles from which arsenic can be profitably recovered. (7,8) High arsenic levels have been encountered in raw muni cipal water suppl ies, necessi tating arsenic removal by the water treatment industry. 2847E 30 FIGURE 2.4- I WASTE REDUCTION COMPONENTS RECYCLABLE PRODUCT A I ENDPRODUCT I I I OR WASTE WASTE REDUCTION WASTE TREATMENT I RECYCLING Ib I T I c RECYCLABLE I DISPOSAL ON PRODUCT SITE ON SOURCE SITE CENTROL IMPROVED FACILITY PRODUCT CLEANLINESS MODIFICATION SUBSTITUTION < Only limited information was encountered on current levels of arsenic in industrial wastes , and on current treatment processes and removals ~btained"~,~~).Most recent industrial literature(6* 15), whi 1e referring to arsenical wastes and to the severe pollution resulting from thei r discharge, presents no specific treatment processes or industri a1 waste values. More up-to-date information is available on the removal of arsenic from drinking water, and in fact the methods for arsenic treatment of both drinking water and industrial wastes are similar. (12) The treatment methods and arsenic removal efficiencies di scussed in detai 1 below are summarized in Table 2.4-1. No treatment costs directly related to wastewaters were encountered in this literature search. Effluent arsenic levels of 0.05 mg/l are obtainable by use of precipitation of the arsenic as the sulfide, by addition of sodium or hydrogen sulfide at pH 6-7'13). Polishing of the effluent by sand filtration would presumably be required to meet the quoted effluent level. Two common water treatment methods have been found to be effective in arsenic removal , they are lime precipitation and carbon adsorption. The lime process was found to reduce an initial arsenic level of 0.2 mg/l down to approximately 0.03 mg/l. Absorption through a charcoal bed yielded an effluent containing 0.06 mg/l of arsenic. (29) Arsenic reduction in a conventional water treatment plant employing coagulation, settling, and filtration has been reported(18). Ferric sulfate employed as a coagulant, was able to reduce the arsenic content of the water from 25 mg/l down to 5 mg/l or less. Lund has suggested that the basis of this arsenic removal method is that arsenic is complexed with heavy metals and thereby removed when the heavy metal pre~ipitates'~). In the Buswell study described above(18), the arsenic would thus be complexed and removed by precipitation with the ferric hydroxide formed upon addition of the coagulant, ferric sulfate. 2847E 31 TABLE 2.4-1 SUMMARY OF ARSENIC TREATMENT METHODS AND REMOVALS ACHIEVED Initial Final Percent Treatment Arsenic, mg/l Arsenic, mg/l Removal Reference Lime Softening 0.2 0.03 16 Precipitation with Lime --- - Charcoal Fi1 tration 0.2 0.06 16 Ferric Sulf de Filter Bed 0.8 0.05 11 Coagulation with Ferric 25.0 -<5 18 Sulfate Coagul ation with Ferric 3.0 0.05 20 Chloride Precipitation with Ferric --- 0.6 19 Hydroxide Precipitation with 362.0* 15-20* 4 Ferric Hydroxide Precipitation with --- 0.05 13 Sulfide Salt *as arsenious oxide 2847E 32 Vi ni egra and Marquez (lo)have also employed ferric hyroxide to effectively remove arsenic from water suppl ies. Their treatment sequence involved addition of ferrous sulfate for precipitation, and subsequent filtration. Effluent arsenic levels less than 0.05 mg/l was the goal of the treatment Drocess. Simi lar treatment of arseni c-contami nated water has been reported. (9,191 Various standard treatment methods were evaluated for removal of arsenic with coagulation partially effective. Passage of the water through a ferrous sulfide filter bed, followed by addition of bone carbon, settling, and filtration reduced the level of arsenic from 0.8 to 0.05 mg/l. Passage through ferrous sulfide followed by settling and filtration through sand and coke reduced the concentration from 0.8 mg/l to "only a trace. ll(22) Ina written discussion, Irukayama provided data on removal of arsenic by the use of firric chloride coagulant(20). Ferric chloride was added after adjustment of the water pH to 10.3 by slaked lime, Ca(OHI2. Ferric hydroxide precipitate formed, and was removed by filtration. Lund has reported that arsenic in an industrial waste which also contains heavy metals in solution can be concurrently removed with precipitation of the heavy metals. Approximately 90 percent reduction of arsenic is to be expected (16*23). A patented waste recycle process (15) removes arseni c and cadmium simultaneous with the precipitation of iron as ferric hydroxide. This is based upon the same removal mechanism described by Lund for industrial wastes, and discussed in some detail above with respect to removal of arsenic from drinking water. Cherinski i and Gi n~hurg'~)have also described the use of this technique in reducing an arsenic level of 362 mg/l (as arsenious oxide) to 15 20 mg/l. Ferrous sulfate and lime were added to the waste, which originated from a pesticide manufacturing process. Ferric hydroxide was removed by settling. Arsenic removal from wastewaters from the rare-earth industry, Skripach, & ,1.(34)have reported that arsenic can be effectively removed by lime addition, but only in the presence of iron. (3) Similar experience was described by Ni 1sson(20) , who was unable to achieve effluent arsenic levels below 9.7 mg/l through lime treatment of a low iron water. 33 Maruyama, g& al.,(14) performed extensive pilot plant studies on physica chemi cal removal processes for arsenic in municipal wastewater. Thi s treatment process involved addition of a coagulant, followed by flocculat on and settling, dual-media filtration, and carbon adsorption. Types and 1eve1 s of coagulants employed are given in Table 2.4-2. Treatment results for an initial arsenic concentration of 5 mg/l are reported in Table 2.4-3. For th s wastewater, filtration provided little or no improvement, although carbon column polishing was effective in all cases. No costs directly bearing on arsenic removals from either drinking waters or waste waters were encountered in an extensive search of the literature. However, the most effective, and most commonly reported arsenic treatment process is one quite similar to that employed in treating drinking water. This is coagulation, sedimentation, and filtration. If the arsenic-bearing waste is acidic, pH adjustment to an alkaline condition may be required, and additional chemical costs are associated with that. Adjustment of pH is most frequently by use of lime, also employed in water treatment. Arsenic is used as a raw material and produced as a waste in a variety of industrial processes. There appears to be extremely little information available in the current literature on industrial waste levels and on industrial waste treatment processes. Removal of arsenic from municipal waters has been more widely reported. Arsenic treatment processes for both municipal waters and industrial wastes seem to be similar and basically involve coagulation to produce a ferric hydroxide precipitate which can then be filtered. This process has consistently yielded effluent arsenic levels of 0.05 mg/l or less. The treatment processes employed all deal with soluble arsenic. In almost every case, filtration or other solid-liquid separation is required once the arsenic is in an insoluble form. 2.4.3 FILTRATION(31 1 Suspended solids are separated from fluids via three mechanisms: inertial impaction, diffusional interception and direct interception as illustrated in Figure 2.4-2. Both inertial impaction and diffusional interception are 2847E 34 TABLE 2.4-2 TREATMENT SYSTEMS FOR ARSENIC REMOVAL (14) System Coagu 1ant PH Iron Ferric Sulfate @ 45 mgll Fe 6.0 Low Lime Lime @ 260 mg/l 10.0 Ferric sulfate @ 20 mg/l Fe High Lime Lime @ 600 mg/l 11.5 TABLE 2.4-3 PILOT PLANT ARSENIC REMOVAL (14) Effluent Cumulative Percent Removal Concen t rati on System Settling + Filtration + Carbon mg/l Iron 90 89 96-98 0.06 Low Lime 79 79 82-84 0.92 High Lime 73 75 84-88 0.77 2847E 35 I E FIGURE 2.4-2 MECHANlSMS OF FILTRATION FLUID FLOW STREAMLINES FIGU RE 2.4-3 BETA VALUES IN USE 1 much less effective with liquids than with gases. Since the density of a particle will typically be closer to that of a liquid than to that of a gas, deviation of a suspended particle from the liquid flow line is much less, and this impaction on the structure of the medium is less likely. Diffusional interception in liquids occurs to only a very limited extent because Brownian Motion is not nearly as pronounced in liquid suspensions as in gaseous suspensions. While inertial impaction and diffusional Interception are not effective in liquid service, direct interception Is equally as effective In both liquid and gas service and is the primary mechanism for separating particles from liquids. Direct interception is easily understood in the case of a woven wire mesh filter with uniform pores and no thickness or depth; once a particle passes through an opening, it proceeds unhindered downstream. Yet such a filter will collect a very significant proportion of particles whose diameter is smaller than the openings or pores of the medium. Several factors such as irregular particle shapes, bridging, and surface interactions help account for this collection. Every type of filter will collect particles finer than its absolute rating, and under extreme impulse conditions such finer particles may release. Filters in which the structural portions of the medium are free to move in response to increased pressure are particularly prone to this occurrence, and they may even release downstream particles larger than their pore size. In a well-designed filter, particles larger than the pore size do not pass downstream of the medium. The most successful approach to zero particle release is achieved by using a filter medium in which the pores will not enlarge under pressure and in which the thickness is sufficient so that in normal service substantially all the incident particles are collected in the first tenth to fifth of the thickness, leaving the rest available to stop undersize particles which may be released from the upper layer on impulse. 2847E 36 Aids to Liquid Filtration It is possible to supplement the three principal mechanisms of filtration, and to enhance a filter's effectiveness in removing particles from a liquid. Several methods include electrostatic deposition, flocculation and fi 1ter aids. Most particles carry a negative charge. It is possible therefore to enhance the particle capture mechanisms of a filter by inducing a desired charge (usually positive) on the filter. But, one must use great caution when seeking to aid the filtration of liquids through electrostatic deposition. These charges are often unstable and influenced by pH of the contacting fluid, time, and the deposition of charged particles. Flocculation is one way to enhance filterability by causing fine particles to "clump" together to form larger particles that are easier to filter. Flocculation of particles by the addition of polyelectrolytes (long chain molecules .with many positive and negatively charged ionic points along the chain length) to the fluid system is a common practice. Polyelectrolytes such as soluble starches, gelatin, and derivatives of polyacrylates attach themselves to many oppositely charged particles in the liquid causing their agglomeration and increasing their settling rate. They should be selected empirically for each fluid process. Whether or not a polyelectrolyte can be used in a filter process depends on its performance and cost. The ease with which fine size particles can be removed from a liquid stream can also be increased by the addition to the suspension of small amounts of filter-aids. This is known as a "body feed" or "body aid", and should not be confused with precoat filtration where filter aid is first deposited on a filter and the suspension then caused to flow through. Perhaps the most commonly used filter-aid is diatomaceous earth, which consists of the sedmentary deposits of fossilized diatoms. The diatom skeletons have a wide variety of shapes, and it is this property which 2847E 37 enables them to produce filter cakes of high permeability. Other filter- aids include perlite (an igneous rock formed by the quenching of molten volcanic lava in water), carbon, and cellulose. Filter aid filtration is not common in fluid clarification but, when used, is often found upstream of cartridge filtration. Cartridge filters are used as "trapt1 filters downstream of precoat filters to capture any filter aid which may "bleed" past the filter medium. Fi 1 ter TYDes In recent years it has become increasingly common to classify filters and fi 1 ter media as either "depth type" or Ilsurface type". Unfortunately, filter manufacturers have been unable to agree upon an "official" definition of the terms. As a result, much misunderstanding is encountered in the field on this subject. A better classification is whether the media is fixed or not fixed under changing pressure conditions. Non-Fixed Random Pore DeDth TyDe Media Non-fixed random pore depth type media depend principally on the filtration mechanisms of inertial impaction and/or diffusional interception to trap particles within the iterstices or spaces of their internal structure. Examples of this type of media are felts, woven yarns, asbestos pads, and packed fiberglass. These fi 1 ters are, therefore, not usually used for liquid service. Fixed Fixed random pore depth type filters consist of either layers of medium or a single layer of medium having depth, depend heavily on the mechanism of direct interception and are so constructed that the structural portions of the medium can not distort. 2847E 38 Removal Rat! nas Various rating systems have been evolved to describe the filtration capabi 1 iti es of fi1 ter elements. Unfortunately, there is no general ly accepted rating system and this tends to confuse the filter user. Several of the systems now in use are described below. Nomi nal Rat! nq Many filter manufacturers rely on a Nominal Filter Rating which has been defined by the National Fluid Power Association (NFPA) as: "An arbitrary micron value assigned by the filter manufacturer, based upon removal of some percentage of all particles of a given size or larger. It is rarely well defined and not reproducible." In practice, a "contaminant" is introduced upstream of the filter element and subsequently the effluent flow (flow downstream of the fi1 ter) is analyzed microscopi cal ly. A given Nominal Rating of a filter means that 98% by weight of the contaminant above the specified -size has been removed; 2% by weight of the contaminant has passed downstream. Absol Ute Rati nq The NFPA defines Absolute Rating as follows: "The diameter of the largest hard spherical particle that will pass through a filter under specified test conditions. It is an indication of the largest opening in the filter element. Such a rating can be assigned only to an integrally bonded medium (such as a fixed pore depth media or sintered metal media). There are several recognized tests for establishing the Absolute Rating of a filter. What test is used will depend on the manufacturer, on the type of medium to be tested, or sometimes on the processing industry. In all cases the filters have been rated by a "challenge" system. A filter is challenged by pumping through it a suspension of a readily recognized contaminant (e,g. glass beads or a bacterial suspension), and both the influent and effluent examined for the presence of the test contaminant. 2847E 39 Beta Ratina System While absolute ratings are clearly more useful than nominal ratings, a more recent system for expressing filtration rating is the assignment of Beta Ratio values. Beta Ratios are determined using the Oklahoma State University, "OSU F-2 Filter Performance Test." The test, originally developed for use on hydraulic and lubricating oil filters, has been adapted for rapid semi-automated testing of fi 1ters for service with aqueous liquids, oils, or other fluids. The rating system measures the total particle counts at several different particle sizes, in both the influent stream and effluent stream. A profile of removal efficiency emerges for any given filter. Figure 2.4-3 illustrates this principle. Choosing the ProDer Fi1 ter Among the -more important factors tllat must be ,aken into consideration when choosing a filter for a particular application are the size, shape, and hardness of the particles to be removed, the quantity of those particles, the nature and volume of fluid to be filtered, the rate at which the fluid flows, whether flow is steady, variable and/or intermittent, system pressure and whether the pressure is steady or variable, available differential pressure, compatibility of the medium with the fluid, fluid temperature, properties of the fluid, space available for particle collection, and the degree of fi 1tration required. Nature of Fluid The materials from which the medium, the cartridge hardware, and the housing are constructed must be compatible with the fluid being filtered. Fluids can corrode the metal core of a filter cartridge or a pressure vessel, and the corrosion will in turn contaminate the fluid being filtered. Thus it is essential to determine whether a fluid is acid, alkali, aqueous, oil or solvent based, etc. 2847E 40 F1ow Rate Flow rate is dependent on two general parameters, pressure and resistance. Flow rate depends directly on pressure and inversely on resistance. All other factors being equal, if the pressure on a fluid is increased, then the flow rate of that fluid will increase. Viscosity is the resistance of a fluid to the motion of its molecules among themselves or a measure of the thickness or ability to flow of a fluid. Water, ether, and alcohol have low viscosities; heavy oils and syrup have high viscosi ties. Vi scosi ty affects res1stance directly. If a1 1 other conditions remain constant, doubling the viscosity in a filter system gives twice the original resistance to flow. Consequently, as viscosity increases, the pressure required to maintain the same flow rate increases. TemDerature The temperature at which filtration will occur can affect both the viscosity of the fluid, the corrosion rate of the housing, and filter medium compati- bility. Viscous fluids generally become less viscous as temperature increases. Thus, it is important to determine the viscosity of a fluid at the temperature at which filtration will occur. Pressure DroD Everything a fluid passes through or by contributes resistance to the flow of that fluid in an additive fashion. The pressure losses due to flow of the fluid through the tubing, piping, etc., couples with the pressure loss through the fi 1ter to produce resistance. Resistance to flow through a clean filter will be caused by the filter housing, cartridge hardware, and the filter medium. For a fluid of given viscosity, the smaller the diameter of the pores or passages in the medium, the greater the resistance to flow. When a fluid meets resistance in the form of a filter, the result is a drop in pressure downstream of that 2847E 41 filter, and the measurement of the pressure drop across the filter is called the differential pressure. Thus, for all practical purposes the terms pressure drop, differential pressure, are synonymous. The more resistance a filter medium offers to fluid flow, the greater the differential pressure at constant flow. In the preceding discussion it was tacitly assumed that the fluid was completely free of particulate contamination. But in reality there will always be some particles present in a system. As the filter does its job, particles will be stopped by and partially occlude or block the pores or holes of the filter medium, thereby increasing resistance to flow. In choosing a filter, therefore, one must provide for sufficient pressure source not only to overcome the resistance of the filter, but also to permit flow to continue at an acceptable rate as the medium plugs so as to use fully the effective dirt holding capacity of the filter. If the ratio of the initial clean pressure drop through the filter to total available pressure i-s disproportionally high, unacceptable flow will quickly result even though the medium's capacity for collecting dirt has not been exhausted. When this occurs, the proper solution is usually to increase pump capacity or gravity head, or as an alternative, to reduce clean pressure drop by increasing filter size. Fi1 ter cartridges exhi bit an exponenti a1 ly increasing pressure drop vs. dirt capacity of the filter is mostly consumed before the sharp increase in pressure drop. Consequently, the available system pressure source should be at least sufficient to overcome the pressure drop so as to utilize most of the dirt holding capacity of the filter medium. In choosing a pressure source, one must take into consideration the res1stance to flow of the fi1 ter-both constant res1stance components (fi1 ter housing and element hardware) , and the variable resistance components (filter cake and medium). As filtration proceeds at constant flow, there will be an increase in pressure drop made up of a constant component and an increasing variable component. Eventual ly, the increasing pressure drop 2847E 42 component becomes so large as to either clog the filter and stop flow or to structurally damage the filter. Enough pressure drop should be available to satisfy both components at least to filter clogging. Surface Area The life of most screen and fixed pore depth type filters is greatly increased as their surface areas are increased; in fact, the ratio can be as much as the square of the area ratio. From the foregoing it is apparent that an increase in surface area will yield at least a proportional increase in service life. Under favorable circumstances, the ratio of service life may approach the square of the area ratio. In many, if not most cases, a filter user will save money in the long run by paying the higher initial cost of a larger filter assembly. As the surface area is increased, a larger housing (container or pressure vessel) is required. There is, of course, a practical limit to housing size. It- is for this reason that filter manufacturer uses convoluted or pleated structures to provide large surface areas in small envelopes, thereby keeping housing size and cost to a minimum. Void Volume Void volume, or the open area of a medium, is always of great importance. All other factors being equal, the medium with the greatest void volume is most desirable because it will yield longest life and lowest initial clean pressure drop per unit thickness. As the fiber diameter decreases, the void volume increases, assuming constant pore size. Other factors, however, such as strength, compressi bi 1 i ty as pressure i s applied (which reduces void volume), compatibility of the medium with the fluid being filtered, cost of medium, cost of constructing that medium into a useable filter, etc., must all be considered when designing a filter for a particular application. 2847E 43 Dearee of Fi1 tration The filter chosen for a given application must be able to remove contamination from the fluid stream to the degree required by the process involved. Once the size of the contaminants to be removed has been determined, it is possible to choose a filter with the particle removal characteristics needed. Choosing a filter with a pore size finer than required can be costly because the finer the filtration, the more rapid the clogging and the higher the cost. One should select a medium which will not change Its structure under system-produced stress because as system pressure rises to accommodate flow as filter cake builds, strands of woven wire mesh must not separate to produce a larger pore. When it is necessary to support thin, membrane-type filters, attention must be given to the characteristics of the support material chosen. Support materials can react with the fluid, add significant resistance to flow, and cause shorter filter life. Prefi1 tration The purpose of a prefilter is to reduce overall operating cost by extending the life of the final filter. Extending final filter life may not in itself be sufficient to justify prefiltration; overall cost reduction is usually the principal consideration. Most applications are better served by increasing final filter area rather than by providing a prefilter. This is because increasing final filter area jilwavs yields a longer cycle and lower operating costs. Doubling the area of the final filter will result in two to four times the life. Thls approach also results in lower costs, requires less labor input, and permits operation with less power at lower pressure drop. Cost is less because one housing is used instead of two, and cost is further reduced because the larger filter installation has life in service which is proportionally larger than the increase in area. Clean pressure drop is reduced because of larger area, whereas a prefilter always increases pressure drop. Power required is reduced because pressure drop through most of the filtration cycle is lower. 2847E 44 Selection of filtration equipment such as those illustrated in Figure 2.4-4 requires a great deal of specific process information. Such information as particle distribution of solids, the amount of solids, the wastestream flowrate, pH, temperature pressure etc. all impact proper filter design and specification. Figure 2.4-5 is an engineering figure used for selection of the filter type based on process information. 2.4.4 PRECIPITATION WITH SODIUM SULFIDE(25) Sulfide precipitation is an effective process for the treatment of industrial wastes containing highly toxic heavy metals. The attractive features of the sulfide precipitation process are: attainment of high degree of metal removals over a broad pH range, effective precipitation of certain metals (such as: As, Cu, Cd, Hg) even at very low pH, low detention time require- ment in the reaction tank because of the high reactivity of sulfides, and the feasibility of selective metal recovery. With sulfide precipitation, the high reactivity of sulfides with heavy metal ions and the very low solubiliti-es of the heavy metal sulfides over a broad pH range are features not found with the hydroxide precipitation processes. Industries engaged in metal finishing or metal production operations use large quantities of contact process water, and the spent process wastewater streams contain moderate to high concentrations of As, Cd, Cu, Zn, Pb, Hg, etc. Various physi cal-chemi cal treatment methods to remove heavy metals have been reported in the literature. Hydroxide (lime) precipitation of heavy metals followed by settling of the precipitates is most often used to treat industrial wastewaters. However, the minimum solubilities for different metals occur at different pH values and the hydroxide precipitates are amphoteric in nature and thus maximum removal efficiency of mixed metals cannot be achieved at a single pH. Sulfide precipitation (with Na2S or NaHS) processes used to remove heavy metals have gained considerable importance. Arsenic separation behavior is particularly emphasized because of its importance to the microelectronics industry as well as the non-ferrous metal production industry. 2847E 45 .. uo!suedxa pue i!)oJiai Jo4-iua!uanuoa aJe sassa~dJ31ll FIGURE 2.4-5 SELECTION OF SEPARATION PROCESS BY PARTICLE SIZE & CONTAMINATION LEVEL APPROXIMATE RANGE CONTAMINANT LE VEL* A NGST R 0 M/MI C,R 0 N I % SOLIDS IN FEED PROCESS CARTRIDGE --HOLLOW PAPER 1 --MEMBRANE --PLEATED MEDIA --SINTERED METAL --YARN WOUND --MOLDED --WOVEN WIRE CENTRIFUGE CYCLONE FILTER PRESS FLAT BED ION EXCHANGE LEAF REVERSE OSMOSiS STRAl NE R VACUUM DISK VACUUM DRUM (Precoat) ~~~~ 0 CONTAMINANT LEVEL SHOULD BE FILTRATION RANGE R.O. ULTRA MICROFILTRATION MINIMIZED BY PREFILTRATION WITH MORE ECONOMICAL METHOD I I I I 0.1%=1000 PPM Sulfide PreciDi tation Reactions Most heavy metal sulfides have very low solubilities, even at acidic pH values. HgS (Ass3, CuS, CdS, and PbS can be completely precipitated even at pH 2. The extent of metal sulfide precipitation Is a function of pH, type of metal, sulfide dosage, and other interfering ions that might be present. The primary reactions between As(ll1) and sulfide are listed in Table 2.4-4. Arsenic precipitates only in acidic pH with the solubilities of other metals decreasi ng as pH increases. Metal hydroxi de precipitate sol ubi 1i ties are considerably higher than the corresponding sul fide preci pitates and the precipitation of hydroxide occurs only in a narrow pH range. With sulfide precipitation, a residual concentration less than 0.1 mg/l metal (for Cu, Cd, Pb, and Zn) could be achieved at 4 5 pH 5 12. A full-scale plant was put into operation in 1978 and was designed to precipitate (at pH 3-51 As, Zn, Cu, Pb, Cd, and Hg as sulfide at acidic pH for possible recovery of metals and to remove fluoride separately by lime (at pH < 10) as CaF2 for landfill of Hewlett-Packard's arsenic were principle soluble, this process would be almost identified. A schematic diagram of the process is shown in Figure 2.4-6. The wastewater was first partially neutralized (to pH 2.5 - 3.0) with NaOH, and then Na2S (as 15% Na2S solution) was added and controlled by monitoring pH. The sulfide precipitate was removed by sedimentation (after polymer addition) and post-filtration. The wastewaters treated also contained fluoride, which was removed by precipitation with lime following sulfide precipitation. Bench-scale sulfide precipitation experiments were conducted with three actual scrubber wastes (Table 2.4-5) obtained from a copper smelting operation. The wastes contained high concentrations of heavy metals, iron, and arsenic. Previous studies with actual smelter effluents have shown that high heavy metal removal efficiencies can be achieved by precipitation with sodium sulfide followed by separation of the sludge from the clarified wastewater. Arsenic removal was dependent on the wastewater 2847E 46 TABLE 2.4-4 ARSENIC (111) - SULFIDE PRECIPITATION REACTIONS Reactions As2S3 (SI + 4 H20 -----><----- ZHAs02 + 3 HZS -----> H+ + AsOp - HAs02 <----- 2 As2S3 (SI + 2Hz0 -----<----- > 3 H+ + As3Si- + HAs02 AszS3 (SI + S2’ 2847E 47 TABLE 2.4-5 ANALYSIS OF ACTUAL SCRUBBER BLOWDOWN WATERS Con c en t rat ion Parameter Batch I Batch I1 Batch I11 PH 1.65 1.80 2.80 As 100 mg/l 307 mg/l 612 mg/l Se 3.0 mg/l 2.8 mg/l 1.5 mg/l Cd 10.5 mg/l 12.0 mg/l 15.0 mg/l Zn 86 mg/l 202 mg/l 175 mg/l cu 297 mg/l 792 mg/l 1600 mg/l Fe 149 mg/l 441 mg/l 122 mgll Pb* 39 mg/l 142 mg/l 62 mg/l Hg 2.0 mg/l 1.5 mg/l - s04 700 mg/l 1300 mg/l 2700 mg/l *91% of Pb is present as Insoluble lead (Pb SO4). 2847E 48 characteristics. Since arsenic precipitates only at low pH values this study was directed to establ ish the possi bi1 ity of simultaneous removal of arsenic (by adsorption on precipitates or by Fe-As interaction) and heavy metals at alkaline pH values with Na2S dosage 5 1 .Ox. Sulfide precipitation experiments with the three scrubber wastes (Table 2.4-5) were conducted after initial pH elevation (with lime slurry) to 5.0 - 6.0. The sulfide precipitation reaction pH was varied between 7.5 - 8.5. The metal separations obtained with Batch I and Batch I1 wastes were quite similar; but with Batch I11 waste the arsenic separation was considerably poorer than the results obtained with Batch I or Batch I1 wastes. For both Batch I and Batch I1 wastes 98-99.6% metal (including As) removals were obtained at 0.6X dosage and pH 8.0. With Batch I11 waste, variable sulfide dosage studies again indicated 0.6X to be optimum dosage, but arsenic removal was only 83%. Studies showed that the value of the molar ratio of Fe/As in the raw waste determined the extent of arsenic separation. In an effort to understand the effect of Fe+3 on arsenic separation, several experiments were conducted with normal wastes without Fe+3. The results in Table 2.4-6 show that arsenic removal dropped considerably in the absence of Fe+3. With less than theoretical sulfide dosage, Fe+3 is precipitated as Fe(OHI3 and thus enhances arsenic removal. The decrease in Fe/As ratio from 2.01 to zero caused arsenic separation to drop from 98% to 59%. The molar ratio of Fe/As for both Batch I and Batch I1 wastes were about 2.0 and arsenic removal was excellent. The Batch I11 waste had a molar Fe/As ratio of 2.7 and arsenic separation was only 82%. By increasing the Fe/As ratio of Batch 111 waste to 1.0, arsenic separation increased to 99% (Figure 2.4-7). Figure 2.4-7 shows that arsenic removal is reduced at molar Fe/As less than 0.8. A different type of actual copper plant waste containing arsenic, other heavy metals gave greater than 99% removal of all heavy metals (except arsenic) at the optimum sulfide dosage. The arsenic separation with this waste was only 40% because of the low molar Fe/As ratio (0.13). 2847E 49 TABLE 2.4-6 EFFECT OF IRON/ARSENIC RATIO ON ARSENIC AND HEAVY METAL SEPARATION Removal X Waste Molar Fe As Cd Zn cu Pb Synthetic Batch I type waste 2.01 98.5 99.0 98.6 99.9 99.9 Synthetic Batch I 0 59.0 99.0 99.3 99.9 99.0 type waste without Fe+3 TABLE 2.4-7 ANALYSIS OF INLET WASTEWATERS (FULL-SCALE PLANT) Parameter Concentration, mg/l PH 1.9 - 2.8 A5 130 - 450 Zn 30 - 60 Pb 20 - 40 Cd 3 - 16 cu 3-5 Hg 2-4 Fe 5 - 20 Sulfite (dissolved SO21 600 - 1000 so4 1500 - 2000 Fluoride (F) 90 - 130 2847E 50 Fl G U R E 2.4-6 SULFIDE PRECIPITATION PLANT (BOLIDEN METALL, SWEDEN) "OH w.2 s POLYELECTROLY LE LIME FIGURE 2.4- 7 EFFECT OF RATIO OF FE/AS ON ARSENIC REMOVAL BY A COMBINA TlON H YDROXIDE-SULFIDE PRECIPITA TlON W Ideally, the separation of metals can also be achieved at acidic pH values since metal-sulfide precipitation reactions predominate over H2S formation reactions. However, sulfide addition rates must be constantly controlled or H2S gas would evolve. If wastewaters contain both heavy metals and fluoride, a two-stage precipitation (sulfide to precipitate heavy metals and 1ime to precipi tate f 1 uori de) process would be requi red to precipitate heavy metal s (pl us arseni c) and f 1uori de separately. Since the Bo1 iden plant wastewater contained heavy metals, arsenic, and fluoride, two separate precipitation steps were utilized. The wastewater at the Boliden plant also contained high concentration of dissolved SO2 (sulfite). The major constituents of the inlet wastewater from copper and lead smelting operation were arsenic and zinc with copper, lead, mercury, and selenium present in smaller amounts. For the five full-scale test runs the combined process water and wash water inlet concentration ranges are shown in Table 2.4-7. The sulfide precipitation pH was in the range of 3.7 to 4.8 and the fluoride precipitation pH was in the range of 11.2 to 11.5. Since arsenic precipitates best around pH 3 and zinc precipitation is complete above pH 5, two-step precipitation would be most desirable. The overall removal of a1 1 metal s were excel 1ent with sulfide precipitation followed by lime precipitation. (The ranges of removal of metals by sulfide precipitation only and by sulfide-lime combination process are shown in Table 2.4-8 for the five full-scale test). The inadequate separations (by sulfide precipitation only) of As and Zn obtained in the full-scale tests were due to the wide fluctuations of pH and sulfide dosage and the consumption of a portion of the Na2S reagent by dissolved SO2 (sulfite) present in the wastewater. The control technique of sulfide dosage by pH rise was found to be insufficient for simultaneous arsenic and zinc removal at optimal efficiency. In order to understand the importance of sulfite-sulfide side reaction at acidic pH values, bench-scale studies were conducted with single metal salts in the presence of sulfite at acidic pH values. Depending on the metals studied part of the Na2S was consumed by SO:- to form elemental sulfur and thiosulfate. Even with 2847E 51 TABLE 2.4-8 REMOVAL OF METALS BY SULFIDE PRECIPITATION AND BY SULFIDE PRECIPITATION FOLLOWED BY LIME PRECIPITATION (FULL-SCALE PROCESS) Component Sulfide Precipitation Sulfide + Lime Precipitation As 67 - 87 96 - 99 Zn 51 - 75 99 Pb 97 - 99 97 - 99 Cd 99 99 cu >90 >90 Hg 99 99 Fe 2 - 26 >99 F1 uori de 0 70 - 78 2847E 52 sulfide overdoses at low pH values no H2S gas loss from the solutions 2- occurred (also observed in full-scale tests) due to SO3 - H2S reactions. At stoichiometric Na2S dosages (to form As2S3, ZnS, etc.) the sulfite-sulfide reaction played an important role only during precipitation of As and Zn at low pH values. The effects of sulfide-sulfite reaction were found to be negligible above pH 5. In summary, the feasibility of a combination of hydroxide-sulfide precipitation (at pH 8-9) process, and a process involving sulfide precipitation (at pH 3-51 followed by lime precipitation, is established to achieve a high degree of separation of heavy metals and arsenic. The combination hydroxide-sul fide process required only 60% of the theoretical Na2S dosage to provide effective separations of heavy metals and arsenic. Simple sulfide precipitation at pH 3-4 also provided excellent removals for Cu, Cd, Hg, and Pb. For precipitation of arsenic and zinc sulfide at pH < 5, the side reaction between sulfite (if present in wastewater) and sulfide must be considered. Hydrogen sulfide gas formation was never found to be a problem during precipitation because of the high reactivity of sulfides and heavy metals. (26) 2.4.5 SOLIDIFICATION Many processes have been developed for waste treatment with most aimed at a specific waste stream with known chemical characteristics. The extruder- evaporator system was developed because of the need for a process to handle a variety of chemical properties associated with the relatively low-volume, highly-toxic wastes such as; arsenic, heavy metals or electroplating type wastes. This solidification system is a simple mechanical process where the extruder-evaporator evaporates a1 1 unwanted solvent from the waste while homogenizing the waste constituents with a liquid plastic binder for discharge into a container. Once this waste-plastic mix has cooled, a significant volume reduction effect is realized. In addition to this, the system returns the clean solvent to the plant for reuse, thereby reducing plant makeup requirements. The end product is finely dispersed waste salts in a solidified plastic matrix. 53 This specific system will produce a solidified product with the hazardous constituents, regardless of their chemical characteristics, immobilized in a plastic binder. The flexibility and capability of this system to handle a wide variety of liquid and dry waste feed streams, in conjunction with most plastic binders (asphalt , polyethylene, polypropylene, urea formaldehyde and vinyl polyesters), means that industry has an effective solidification technology available for the treatment of their wastes. In addition to having this flexibi 1i ty, the extruder-evaporator system wi 11 reduce the total volume of wastes produced, thus reducing ultimate disposal costs. A 1arge number of extruder-evaporators are operating worldwide in the chemical, plastics, food and nuclear industries and in hazardous waste stabi 1ization and solidification applications. Operating experiences indi cate minimal routine maintenance is requi red and minimal exposure of personnel to hazardous conditions during operation or maintenance. This system, when incorporated into an actual processing plant, will provide the following advantages: o Removal and recycle of unwanted solvent in the waste, and subsequent stabilization and solidification of the hazardous constituents. o Volume reduction of the end product (up to 80% reduction), thereby reducing disposal requi rements. o Processing capability for handling the wide variety of wastes and a1 lowi ng feeds from many different sources whi 1e maintaining adequate sol idi fication. o A number of binders may be used to meet the needs of the varying chemical character! stics of waste streams. o The extruder-evaporator demonstrates ease of operation as it evaporates solvents, and disperses the remaining waste solids into a plastic matrix in a single step. The end product solidifies upon cool ing. 2844E 54 o Utilization of batch or continuous modes of operation, thus reducing downtime, maintenance requirements and operator attention. o Low operating costs due to reduced waste volume and weight shipped offsite, and low material costs for binder. o The extruder-evaporator has been proven to be reliable in plastics compounding and hazardous waste processing applications. o Dust-free operation at near ambient pressure, thereby eliminating the potential for in-process accidents, leaks and spills. The extruder-evaporator is the major component of the solidification system. However, the complete system is designed to include collection and feed systems, processing, discharge and containment, container handling systems and remote control instrumentation. The system description that follows will reference an asphalt system, as this is the most widely used binder. However, use of other plastic binders would be comparable. Feed System (General) Many types of wastes (slurries, evaporator concentrates, ion exchange resins, chemical drains, sludges, manufacturing residues, incinerator ash, etc.) are handled by separate mixing and pretreatment components. The mixed wastes are then metered into the inlet barrel of the extruder-evaporator along with a controlled flowrate of plastic binder. The ratio of binder-to-waste is predetermined to maintain an end product of 50% waste salts and 50% asphalt, by weight. Binder Feed (AsDhal t) An asphalt storage tank is located in an easily a essi bl re , near the solidification system and truck delivery access. The tank is sized to accommodate a bulk truck shipment of hot liquid asphalt to optimize del ivery, storage and operational requirements. The hot asphalt remains in a liquid state by maintaining its temperature during storage above 250°F. 2844E 55 The asphalt feed system including transfer and metering pumps, strainers, heat tracing and instruments and controls is designed for operation from a main control panel. Wastes The solidification system includes a separate feed handling, conveying and metering system for each type of waste. Each feed system includes the requi red tanks , mixers * transfer pumps metering pumps * feed conveyors , piping, valving, instruments and controls. These feed systems are interlocked to prevent wastes from being fed to the unit without the extruder-evaporator screws turning, containers in place, or asphalt flowing. Processing The processing operations (volume reduction and mixing) are accomplished in a motor-driven twin-screw extruder-evaporator. Twin co-rotating screws are utilized to mix and convey the waste product and immobilizing agent along the length of the machine. The housings or barrel sections in which the screws rotate are heated to evaporate free and entrained solvent from the mixture. The solvent removed from the feedstream is condensed in the steam (vent) domes, and recycled to the plant. The asphalt and waste are fed to the extruder-evaporator in the first barrel, with the waste slightly downstream of the asphalt. The waste salts and the asphalts are kneaded into a homogeneous mix with asphalt. Entrained liquid is evaporated up through the subsequent steam domes and recycled back to the plant. The homogeneous mix of asphalt and waste is then discharged into a container for di sposal . OPERATING EXPERIENCE The extruder-evaporator system is said to be one of the most extensively researched liquid waste solidification processes. European users claim the asphalt stabilization and solidification process is superior to the process 2844E 56 previously used (cement, cement silicate mixes, and urea formaldehyde) for a variety of reasons, i.e., volume reduction, cost savings, compatibility with waste feeds, superior end product, etc. Application of this system to the fixation and encapsulation of arsenic-laden wastes was tested by JBF Scientific, Wilmington, Massachusetts, under Contract No. 68-03-2503 from the U.S. EPA. Analysis results showed that there are great differences existing among the various processes. In general, the asphalt stabilized, and solidified samples showed a leach rate approximately two orders of magnitude below that of the next best method. Preliminary results of this study were presented at the Hazardous Waste Land Disposal Symposium in San Antonio, Texas on March 8, 1978. 2.4.6 ION EXCHANGE (32) Packed beds of anion exchange resins in the chloride form may be utilized for selective removal of heavy metal contaminants from water. Using nitrate removal as an example, the exchange reaction of interest is: RCL + NO3---+ RN03 + CL- where R denotes the resin phase. The reaction is reversed and the resin regenerated using a concentrated (typically 12 percent) solution of NaCl. The usual operational sequence is exhaustion, backwash, regeneration, displacement rinse and fast rinse. Typical package-type (50-200 gpm) ion-exchange resin beds are 3 to 6 ft. deep by 2 to 5 ft. diameter and contain 20 x 50 mesh resin beads. Typical exhaustion flow rates are 1-5 gpm/cu ft. Regeneration flow rates are much lower at 0.25-0.50 gpm/cu ft. with a minimum regenerant contact time of 45 minutes. The length of a run to nitrate, arsenic or selenium breakthrough is determined mainly by the concentration of competing ions in the feedwater and the resin's preference for the contaminant ion compared to the other ions present. The higher the level of competing anions the shorter the ion exchange run; and the higher the resin preference for the contaminant ion 2844E 57 the longer the run. In the treatment pH range of 6.5 to 8.5 the commercially-available strong-base anion exchange resins prefer the ions of interest in the following order in dilute waters, 1.e.. less than approximately 700 ppm TDS. SO4 >Se04 >Se03 >HAs04 >NO3 >HSe03 FC1 >HC03, FH2As04 >F >>H3As03 The feedwater ions have been separated into zones which move at different velocities in a constant or proportional pattern toward the column outlet. The preferred species move at a slower rate through the column than do the nonpreferred species. The concentration velocity of any species is a function of the bulk fluid velocity and the slope of its equilibrium isotherm. In our nitrate example, when the nitrate zone reaches the column outlet, an abrupt increase in nitrate is observed in the effluent and the run is terminated. An important fact to consider in ion exhcnage equipment design is that all species except the one most preferred will have effluent concentrations greater than influent concentrations after breakthrough. From the selectivity sequence shown above it is evident that all the inorgani c contami nants are 1ess preferred than the ubi qui tous sulfate ion and, therefore, may be concentrated in the product water in this manner. Thus , the breakthrough point must be anticipated and not exceeded. Ion exchanae resin selectivity considerations At least 40 different anion exchange resins are commercially available for single-bed or two-bed (strong-acid cation/weak-base anion) system designs. Many of these resins have been evaluated on a lab scale or on a pilot scale for nitrate removal applications. The EPA is carrying on continuing in-house and other research to determine the best resins for removal of all the inorganic contaminants amenable to ion exchange. A1 though the previously given sel ectivi ty sequence is general ly appl icab1 e to a1 1 the commercially available anion-exchange resins, the design engineer 2844E 58 has some control over the magnitude of the various preferences (separation factors) of one ion over another. For example, Clifford has shown that resins with closely-spaced exchange sites can have enormous preferences for divalent compared to monovalent ions. It has been pointed out, however, that these enormous divalent preferences don't translate into easily grasped, common-sense rules regarding column performance. For example, given the usual resin preferences for sulfate over nitrate, resins with the highest sulfate selectivities may actually be preferred in nitrate removal applications. Reqeneration considerations in ion exchange In the usual ion exchange processes like water softening, countercurrent flow regeneration is more efficient than cocurrent regeneration. This is primarily due to "leakage" considerations which may not apply in contaminant removal processes for drinking water. For example, in nitrate removal, a leakage of 1-2 mg/l of NO3-N may be quite acceptable since the MCL is 10 mg/l N03-N-. On the other hand, excessive nitrate leakage, e.g., 5-10 mg/l N03-N, is undesirable because it substantially reduces the amount of raw water which may be bypass-blended with the treated water. It is a chal 1engi ng engineering problem to minimize the product water cost by optimizing the ion exchange system design and operating conditions. In some cases, the additional equipment compl exi ties required for countercurrent regeneration may be justified but in many situations they probably won't be. Other possibilities to be examined to reduce operating costs are use of high exhaustion flow rates (>5 gpm/cu ft), reuse of spent regenerants, use of different regenerants concentrations and use of different regenerants (e.g., HC1, H2S04, NH40H, NaOH). The use of various regenerants 1 s especially re1evant where regenerant disposal is a probl em and more complex, two-bed, strong-aci d/weak-base, ion-exchange systems are required. The common means of spent-regenerant disposal (for ion exchange and alumina adsorption) are sanitary sewer, stream dilution, deep-well injection, evaporation and dispersion in the ocean. Clearly, the first two a1 ternatives wi 11 be unacceptable in most contaminant removal 2 844 E 59 applications. Ultimate disposal of salty, toxic regenerant solutions remains a major problem for single contaminant removal processes. It is somewhat less of a problem for the desalting process brines since regenerants are not used. However, the volumes to be disposed of from the desalting processes (20-50 percent of product flow) are substantially greater than those for the single contaminant removal processes (4-10 percent of product flow). Ion exchange resins should be considered for arsenic removed but only if the flow stream, arsenic species and variations in pH are absolutely known. For wastewater systems with highly varying conditions, an arsenic removal system able to handle these non-steady state conditions should be considered. 2.4.7 ADSORPTION BY ACTIVATED CARBON (27, 32) Batch studies were performed for a total of 15 different types of activated carbons to determine As(V) removal at various pH values by powdered and granular activated carbons. Most of the Darco carbons showed significant As (VI removal capacity whi le Nuchar and Fi1 trasorb brands exhibited 1 ittle in comparison. Generally, powdered activated carbons had better capacity than granular activated carbon in arsenic removal. Tables 2.4-9 and 2.4-10 give comparisons of adsorption capacity at an optimum pH value of 4 by powdered and granular activated carbons, respectively. The activated carbon D-X demonstrates much better arsenic removal than the other carbons. Among granular carbons, type D-XI is the most effective adsorbent. Both the D-X and D-XI activated carbons were selected for further adsorption studies. It is also found that the removal of As(V) species by activated carbons is markedly affected by the pH value. This can be attributed to the fact that the concentration distribution of arsenic(V) species and the development of surface charge on the activated carbon are pH-dependent phenomena. As the system pH changes, the speciation of arsenic(V) and the carbon surface charge vary. H2As0i and HAsO;-are the predominant species in the pH range studies (3 to 11). 2844E 60 TABLE 2.4-9 COMPARISON OF ADSORPTION CAPACITY BY VARIOUS TYPES OF POWDERED ACTIVATED CARBONS 7'0 AS(V) REMOVED DXI 84.0 DVII I 29.0 DVll 22.0 D-VI 11.0 DIX 11.0 N-l 10.0 N-ll 5.0 BATCH EXPERIMENT CONDITIONS: SODIUM ARSENATE (Na 2HAs04) 5x10 -5 M CARBON DOSE 1 g/L pH=4.0 IONIC STRENGTH 1-0.01 M NaClO 4 REACTION TIME-24 HOURS TABLE 2.4-10 COMPARISON OF ADSORPTION CAPACITY BY VARIOUS TYPES OF GRANULAR ACTIVATED CARBON CARBON % As(V) REMOVED D-X 61 .O N-V 15.0 N-IV 13.0 N-Ill 12.0 F-XII 13.0 F-XIII 7.0 F-XIV 11.0 F-XV 12.0 BATCH EXPERIMENT CONDITION: SODIUM ARSENATE (NaflAsOg 10 -4 M CARBON DOSE 5 g/L pH=4.0 IONIC STRENGTH 1=0.01 M NaClO 4 REACTION TIME-24 HOURS The results indicate that the amount of arsenate removed increases with pH to a maximum value at pH near 4.5, then decreases steadily as the pH increases to the basic range. This is similar to the adsorption of arsenate on aluminum hydroxide and phosphate and silicate on hydrous alumina where a maximum adsorption occurs at a specific pH value then adsorption density decreases with further pH change. Steenburg first used the uptake of inorganic acid and base and the oxidation process to classify activated carbons into "H" and "L" types. Frumkin and Kruyt stated that the activation of carbon at 1000°C either in pure carbon dioxide (C02) or under vacuum, followed by exposure to oxygen at room temperature, results in a hydrophobic carbon surface capable of raising the pH of the solution, which has positive electrophoretic mobility. This type of carbon is what Steenburg called "L" type. By contrast, the oxidation of carbon by exposure to gaseous oxygen at temperatures between 200" and 400°C produces a carbon surface which is able to lower the pH of a solution, is hydrophilic, and has a negative zeta potential. This is a so-called "H" type. The hydrous activated carbon develops its surface charge according to the activity of potential-determining ions (OH- and H30f. A pH value of 7.5 was the zero point of charge. Between pH 3 and 7, which is a1 so the main region of As(W removal , H2As04 is the predominant species. Between pH 7 and 11 where HAsOi-is the major As(W species, significant amounts of As(V) are still adsorbed although not as significant as in the lower pH region. This implies that specific adsorption is the major removal mechanism in addition to electrostatic attraction of the anion. "H" type carbons, like the Darco Series, exhibit a significant adsorbing capacity for AsW. In contrast, adsorption of AsW species by the "L" type activated carbons (such as the Nuchar Series) was poor, probably because of the electrostatic repulsion between anionic As(W species and the negatively charged carbon surface over the pH range studied. 2844E 62 Interferences in adsomtion Iron can drastically enhance AsW removal by Carbon D-XI. Co-precipitation of iron with arsenate on the carbon surface may play an important role in AsW removal. Because the activated carbons that effectively remove AsW such as D-XIII, D-X and D-XI contain significant amounts of ash that may not be amenable to base wash, it has been speculated that the removal of arsenic by these carbons might have some connection with the carbon ash. These carbon ashes were analyzed for moisture, ash content, silicate, calcium, magnesium, iron, aluminum, and phosphate, which are thought to be important to As(V) removal. To find out if silicate has any effect on As(W removal, a suitable amount of silicate was mixed with As(V) solution In the absence of activated carbon. The results, however, show no AsW removal by silicate. Reactivation of Carbon The low adsorption density of As(W by carbon type D-X and D-XI at both ends of the pH scale suggests that arsenic-laden activated carbon can be desorbed by either a strong acid or a strong base. Kinetic data It indicates that chemical regeneration is able to desorb As(V) from the carbon surface. However, reuse of the acid-base treated carbon was not successful. The results indicate that the adsorption capacity of carbon D-X was reduced dramatically after regeneration. One possible explanation is that strong acid and thermal treatment destroy the AsW adsorption sites. SUMMARY The removal of As(V) from water by carbon adsorption is determined by pH, carbon type, and total As(W concentration. Of the 15 different brands of commercial activated carbons tested, two activated carbons, D-X and D-XI seemed to be the most effective. Maximum As(V) removal occurred at pH 4 to 5. Electrostatic attraction and the formation of specific chemical bonds were the major adsorption mechanisms. This was evident from the reversal of surface charge on As(V) adsorption. Treatment with these activated carbons met drinking water standards (0.01 mg/L). 2844E 63 The presence of organics such as Tiron has no effect on As(V1 removal, but the presence of Fe(II1 drastically increased both the rate and the extent of As(V1 removal. Treating As(V1 laden activated carbon with strong acid or strong base effectively stripped off adsorbed As(V1 species from activated carbon surface. However as(V1 adsorption was not restored by strong acid or base treatment. The As(V1 adsorption capacity of the strong acid or base treated activated carbon was greatly improved by further treatment with Fe(II1 salts. Fe(III1, Ca(II1, AL(III1, and Mg(II1 salts did little to enhance As(V1 readsorption capacity, however. 2.4.8 ADSORPTION BY ACTIVATED ALUMINA. BAUXITE. AND CARBON (28,321 Little is known about the adsorption mechanism of arsenic species on activated alumina, bauxite, and carbon. The mechanism relating to the adsorption of arsenate and arsenite ions on amorphous iron hydroxide and aluminum hydroxide was first studied by Ferguson and Anderson. The general conclusion was that the arsenic adsorption mechanism cannot be solely explained in terms of moleclule-surface interaction, electrostatic interaction, or occlusion. The reported zero point of charge values for activated alumina and bauxite are slightly basic. For As(V1, H2As04 - is the predominant species in the pH range between 3 and 6.5. It is apparent that H2As04- is the major species removed by activated carbon. It would not be surprising if this Is a result of the reaction of the monovalent species with the oxo-function groups on the carbon surface as suggested by Huang and Mu. There is probably little affini ty between carbon surface and the nonionic, diVal ent and tri Val ent forms of As(V1. For As(III1, H3As03 is the predominant species in the pH range from 0 to 9. For As(V1 adsorption, negatively charged molecules were removed effectively onto the slightly positive or neutral charge surfaces. For As(III1 adsorption, neutral H3As03 molecules were removed on relatively neutral charged surfaces (could be slightly positive or negati vel. 2844E 64 AdsorDtion Study The three types of activated solids chosen for this study are: 1) 28 X 48 mesh, granular, Activated Alumina; 2) 30 X 60 mesh, granular, Activated Bauxite; 3) 8 X 30 mesh, Activated Carbon. These three adsorbents were not subjected to any additional pretreatment prior to the adsorption study. Experiments were carried out with freshwater, seawater diluted ten times, seawater, and a 0.67 M sodium chloride solution. Trace metals from sodium chloride and seawater were coprecipitated with ferric hydroxide at pH 7.5. These solids were removed by a vacuum filtration technique through an 0.05~ membrane filter. In some cases sodium meta-silcate was added to the freshwater and seawater to evaluate the effect of soluble silicate on the adsorption of arsenic. There is evidence from the analysis of many water samples that both As(II1) and As(W are present under oxidizing as well as mildly reducing conditions. AsW concentrations in geothermal fluids range between 4 and 90 percent of the total soluble arseni c. In general, average As(W concentrations 1 ie between 10 and 40 percent of the total soluble arsenic. Under the mildly reducing condi tions encountered in most geothermal reservoi rs, thermodynami c calculations indicate that arsenic should be present as As(II1). Sergeyeva and Khodskovsky concluded that the most probable form in which arsenic exists in hydrothermal solution (under mildly reducing conditions) is arsenious acid. The existence of both As(II1) and As(W species under these conditions may be a result of incomplete reduction of arsenate to arsenite. The kinetics of arsenate reduction to arsenite are unknown. The existence of both As(II1) and As(V) forms in surface waters is probably caused by the slow rate of oxygenation of arsenite to arsenate or bacterial reduction of arsenate to arsenite at neutral pH in localized areas where a reducing environment can exist. The reaction rate was found to decrease with a decrease in salinity. 2844E 65 Adsomtion kinetics. The results for the adsorption of AsW on activated alumina, bawxite, and carbon in freshwater and seawater shows the rate of uptake of As(II1) by activated alumina and bauxite in freshwater and seawater. In all cases, the adsorption rate is exponential. AsW was found to be removed from solution much faster by activated alumina than by any other adsorbent. Within the first 10 minutes, in fresh water, 50 percent of AsW was removed by activated alumina; 40 percent of As(V) by activated bauxite; and 23 percent of AsW by activated carbon. Rates of As(II1) adsorption on activated alumina and bauxite were much slower than those of AsW. As(1II) removal was found to increase with time in both freshwater and seawater. The rate of adsorption and extent of arsenic removal decreased with increasing sal ini ty. pH Effect. The effect of pH on AsW) adsorption by activated alumina, bauxite, and carbon and As(II1) adsorption by activated alumina and bauxite was studied in the pH range between 2 and 12. Arsenic (VI is effectively adsorbed in the pH range 4 to 7 by activated alumina and bauxite. As(V) adsorption by activated alumina and bauxite was found to decrease above pH7. Activated carbon adsorbs As(V) better in the acidic pH range between 3 and 5 than in other pH values. Adsorption is sharply decreased at both lower and high pH values. Variations in As(II1) adsorption on activated alumina and bauxite over the pH range 4 to 9 were found to be slight. Adsorption decreased sharply above pH 9. These data clearly indicate that activated carbon adsorbs AsW better in the acidic pH range; yet it exhibits poor adsorption capacity in comparison to actlvated alumina and bauxite even at pH 4 (the optimum pH for adsorption on carbon). Effect of solution composition on adsorption. The change in percentage of arsenic removal was found to vary significantly in solutions of different chemical compostions. Arsenic removal is greatly affected by the pH. The percentage of As(II1) removal was greatly affected by the intial As(II1) concentration. However, AsW removal was only slightly affected by the initial concentration level. 2844E 66 The adsorption capacities of various absorbents for As(II1) and As(V) in solution of various chemical compositions were studied with a residual arsenic concentration of 50 pg/l at equilibrium. The data indicates that the adsorption capacity in freshwater and seawater varied as much as 80 percent in some cases. The adsorption capacity for As(V) on activated alumina was found to vary from 4.11 (freshwater) to 0.81 (seawater) mg As(W removed per gram of absorbent. The silica effect on arsenic removal efficiency of various absorbents in freshwater was studied. In general, in comparison with AsW, As(II1) removal efficiency was greatly affected by varying amounts of silica. The effect of silica concentrations on the removal of arsenic is not significantly influenced by the matrix background; however, the matrix background does affect the arsenic removal. It seeems that electrostatic interaction and specific adsorption are important mechanisms for arsenic removal by activated alumina and bauxite. The adsorption study was carried out in solutions of differenct chemical composition to evalute the effect of sodium, calcium, chloride and total ionic strength. The rates of adsorption are shown to be slower in seawater than in freshwater. A1 though rates were reduced with increasing salinity or ionic strength, the adsorption was reduced by no more than 5 percent. As much as 80 percent reduction in the adsorption capacity of activated alumina in seawater (as opposed to freshwater) conditions was observed. A varying degree of salt effect was observed for As(V) and As(II1) adsorption on different adsorbents. In general, As(V) adsorption was affected much more by chemical compostion than was As(II1). The data from this study indicates that As(II1) is less effectively removed than As(V). Oxidation of arsenite to arsenate is necessary to achieve effective arsenic removal. Oxidation of arsenite to arsenate by chlorine has been used successfully to remove arsenic. 2844E 67 2.4.9 ARSINE GENERATION(*) Arsine generation processes while potentially an effective technique for removing certain arsenic forms from wastewater streams, has not found wide acceptance in industry in thi s appl ication according to the 1i terature search conducted. Presumably, the extreme toxicity or arsine gas and the difficulty in containing a toxic gas when compared to containing a toxic liquid or solid is the primary reason for this. A probable second reason is that arsenic compounds are not always in a form in wastewater streams where the arsine gas can readily be formed. Treatment processes required to obtain predominantly arsenic tioxide in water may not be cost effective when compared to the processes for effici ent arsenic removal a1 ready di scussed. 2.5 EVALUATION OF TREATMENT PROCESSES Evaluation of arsenic wastewater treatment processes will focus primarily on their appl icabi 1 ities to Hew1 ett-Packard' s San Jose faci 1 ity. As has been discussed, HP's facility generates primarily a Solid GaAs contaminant with only negligible quantities of soluble arsenic since removal of soluble arsenic sources at HP would not significantly reduce the hazardous waste quantity generated from their HF Treatment system, no process capable of treating only soluble arsenic can be considered effective. Table 2.5-1 lists each potential arsenic removal process along with major evaluation criteria with respect to HP's GaAs process! ng faci 1i ty. The following discussion wi 11 deal with each process individual ly as opposed to discussing each evaluation criterion individually for all processes. Liauid-Sol id SeDaration Fi1 tration(35) Filtration is an extremely efficient means of separating solid particles from liquid streams. This technique has been in use for many years under almost every type of chemical and physical environment. Figure 2.5-1 lists 2844E 68 TABLE 2.51 COMPARISON OF POTENTIAL ARSENIC TREATMENT PROCESSES Potential Overall Potentia1,Waste Potential Costs for HP Potentia1 Form of Arsenic Possible Reduct ion Operational Health Relative to Effect1 veness Most Effectively Applicability to Efficiency for Characteristics and Safety Other Listed in Reducing Arsenic Removal Process Treated Hewlett Packard Hewlett Packard for Hewlet Packard Concerns Procedures Hazardous Waste 1. Liquid - Solid Separation - Filtration Sol id Yes Excellent Excellent Low Lowest Excellent - Centrifugation Solid Yes Excellent Excellent Low Lowest Excellent - Setting Solid Yes Excellent Excellent Low Lowest Excellent 2. Precipitation - Lime Soluble No Low Not Applicable Low Moderate Vivimal - Sodiun Sulfide Soluble No Low Not Applicable Mderate Moderate Minimal - Ferric Hydroxide Soluble No Low Not Applicable Low Moderate Minimal 3. Coagulation - Ferric Sulfate Soluble No Low Not Ppplicable Low Moderate Minimal - Ferric Chloride Soluble No Low Not Applicable Low Moderate Minimal I. Solidification Solid No Low Costly Low High Minimal 5. Adsorption - Ion Exchange Resins Soluble No Low Nct Applicable Low High Minimal - Activated Carbon Soluble No Low Not Applicable Low Hfoh Minimal - Activated Alumina Soluble No Low Not Applicable Low High Minimal - Bauxite Soluble No Low Not Applicable Low High Minimal 6. Arsine Generation Soluble No Low Not Applicable Extreme Hi ah Minima 1 1600E FIGURE 2.5-1 SELECTION OF SEPARATION PROCESS BY PARTICLE SIZE & CONTAMINATION LEVEL APPROXIMATE RANGE CONTAMINANT LE VEL * ANGSTROMIMICRON I % SOLIDS IN FEED PROCESS 1.0 10 100 1000 A0 0.01 01 0.1 1 10 100 0.01 0.1 1 10 100 MICROF .o 1 I I I BAG TYPE (Liquid) CARTRIDGE- I I I I --HOLLOW PAPER --MEMBRANE --PLEATED MEDIA --SINTERED METAL --YARN WOUND --MOLDED --WOVEN WIRE CENTRIFUGE I I I CYCLONE FILTER PRESS -1 I I I I FLAT BED ION EXCHANGE 01 I I I LEAF REVERSE OSMOSiS STRAl NE R VACUUM DISK I I It VACUUM DRUM ...... (Precoat) 0 CONTAMINANT LEVEL SHOULD BE FILTRATION RANGE R.O. ULTRA MICROFILTRATION MINIMIZED BY PREFILTRATION WITH MORE ECONOMICAL-__ - . METHOD I I I 0.1%=1000 PPM just some of the many types of filters available and their main selection criteria. For most liquid flow streams, filtration efficiency can be designed to what ever level is desired. For Hewlett-Packard, a design efficiency of only 60% or better is required to eliminate HP's solid hazardous waste problem with respect to arsenic. This efficiency is easily attained and, therefore, will be at a relatively low cost. Because of the low temperature and pressure conditions in their wastewater stream, design becomes dependent on the particle distribution of the solids present. As this study has been completed, successful installation of effective filtration equipment is a matter of routine chemical engineering practice (32) Operational characteristics of the required filtration equipment like other liquid-solid separation processes would be rather simple and would offer excel 1ent re1iabi 1 i ty with full automatic operation possible. Thi s hands-off operation would reduce health and safety concerns to an absolute minimum. Potential costs to HP for filtration equipment should be among the lowest of treatment processes because of high efficiency, minimal operating and maintenance costs (i.e. no chemical addition or residence time constraints), total automation capability, and the favorable ambient conditions (low temperature and pressure) for filtration. (32) Overall potential effectiveness in reducing arsenic-laden hazardous wastes at HP's facility is excellent and should be among the most effective. Centrifugation and Sedimentation These other solid-liquid separation processes are also very effective and could find possible application at HP's facility. They both share all the positive attributes with filtration. Selection of this equipment over filtration is usually a matter of personal operating preference and available space. All three processes could be equally effective in solids removal if properly designed and operated. (32) 2844E 70 Preci Ditati on Effective arsenic removal can be achieved with these processes if the arsenic form were soluble. Should removal of arsenic from the cleaning and etching wastestreams become desired, this process, like most of the others discussed below, would be very effective. (32) Because this stream now contributes only a negligible portion of the arsenic to the HF Treatment sludge cake, instal lation of such equipment would not be expected. Precipitation processes would be necessarily more expensive than any liquid-solid separation system because precipitation chemicals must be added fol 1 owed by some 1i qui d-sol id separation process. Therefore , it is 1ogi cal to assume that a1 1 systems converting soluble arsenic to some insoluble compound and then reducing that insoluble compound in volume by some means will be more costly to install and operate that most systems requiring only recovery of insoluble arsenic. (33 ,9,261 Because of the above conclusions, precipitation would not appear to be appl icab1 e to HP' s faci 1 ity. Coagulation These processes are very effective in removing soluble arsenic by addition of such chemicals as ferric sulfate or ferric chloride As with the above mentioned precipitation processes, a means of liquid-solid separation is necessary in conjunction with coagulation techniques. In addition, pH adjustment to an alkaline point is usually necessary and would, therefore, add additional operating chemical costs. (11) Coagulation processes would appear to have little utility in removal of insoluble arsenic and is not considered viable for HP's San Jose facility on that basis. 2844E 71 Solidification This process removes the solvent (water in the case of HP's wastewater stream) and mixes the remaining solids and precipitated salts with such binders as asphalt or thermoplastic materi a1 s. The energy requi rements for water evaporation would be very high. Additionally, this process would create additional hazardous waste because of the waste concentration in a large weight of binder. This process is more ideally suited to recovery of radioactive solids and encasement in a volume of inert binder prior to long-term di sposal .(27) Adsomti on These arsenic removal processes are rated the highest in their efficiency with respect to soluble arsenic (and many other ions). If they were used in a wastewater stream with solids present as Is the case for HP, It would act as a filter and is, therefore, not suited for this purpose. Adsorption is commonly used to treat low-levels of soluble heavy metal compounds in wastewaters of many industri es . The processes Droven re1i abi 1 Ity - and efficiency are di scussed ( 17,19,28,27,33) throughout the 1 iterature Arsine Generation Since arsine generation requi s the r ctant t be rseni tri xid in a soluble form prior to generating arsine gas, any costs or processes necessary to convert arsenic compounds to this form would be included in this process. For HP, this would be extremely costly in terms of equipment, chemical additives, energy costs (for acidic conversion to arsenic trioxide) and for gas containment systems. Because HP stresses safety above other process constraints, this type of process would meet with serious obstacles. Therefore, its application for arsenic removal would very limited. 2844E 72 2.6 ENVIRONMENTAL PERSPECTIVE INTRODUCTION Portions of the following discussion address the health aspects of arsenic. Many of the parameters do not pertain to gallium arsenide (GaAs) unless the arsenic in GaAs is converted to free arsenic. In particular, GaAs is much less toxic than free arsenic. (24) Arsenic, may present a health hazard to humans when it is released into the environment as a consequence of an industrial process. The preponderance of clinical and epidemiological evidence regarding the effects of arsenic pertains to trivalent inorganic arsenic. Much of this evidence suggests that trivalent inorgani c arsenic is a carcinogen. Some 1 imited evidence suggests that pentaval ent inorgani c arsenic may a1 so be carcinogenic. The primary routes by which arsenic enters the human body are inhalation and ingestion. Both trivalent and pentavalent arsenic are mutagenic and teratogenic in animal tests. Animal toxicity studies indicate that trivalent arsenic is several times more toxic than pentavalent arsenic. Epidemiological studies of smelter workers show excess lung cancer risk in individuals exposed to arsenic trioxide, and several studies indicate that the risk increases with increasing duration and level of exposure. The currently available experimental and epidemiological evidence does not provide an adequate basis for gauging the effects of chronic low-level exposure to arsenic compounds. It is reasonable to assume that smaller dosages of inhaled arsenic could be involved with the development of cancer, since inhalation is a more efficient route of entry to the body than ingestion. It is difficult to determine a specific level of exposure associated with a specific level of risk because the precision of ambient air measurements is low; the level may be incorrect by as much as one order of magnitude. American Conference of Government-Industrial Hygi en1 sts I~c.~have determined a threshold limit (TLV) of 0.2 mg per cubic meter of air. 2844E 73 California Reaulations for Manauinu Hazardous/Special/Desicmated/ Non-Hazardous Waster California Administrative Code Title 8. C haDter 4. SubchaDter 7: The general industry safety codes (Appendix B) specifies a Permi ssibl e Exposure Limit (PEL) of 10 micrograms per cubic meter of air determined as an average over an 8-hour period. Also, no employee may be exposed to any n or eye contact with arsenic trichloride as skin or eye contact is likely to cause skin or eye irritation. The regulatory requirements of employer responsibility, implementation of health and safety measures, work practices, worker protection plan, housekeeping, signs and labels, employee training program, employee medical exami nation plan, air moni toring and measurement procedures are detai 1ed in Appendix B. California Administrative Code Title 22. Chapter 30: These regulations deal with management of hazardous and extremely hazardous waste. The sections which apply to managing arsenic waste are as follows. Section 66680. This list of chemical names and common names includes arsenic compounds as having potential extremely hazardous properties. Secti on 66699. This section entitled Persistance and Bioaccumulative Toxic Substance, sets limits of Soluble Threshold Limit Concentration (STLC) and Total Threshold Limi t Concentrations (TTLC) for chemical s. Arsenic and arseni c compounds are included on the list. The TTLC and STLC values for arsenic and/or arsenic compounds as set in this section are: STLC 5 mg/l TTLC 500 mg/kg 2844E 74 If the concentrations are less than the TTLC and STLC, limit approvals should be obtained from the Department of Health Services to exempt the waste from management as hazardous waste. Secti on 66472. This section states that all generators of hazardous wastes must obtain an EPA identification number and the wastes should not be offered for transporation or to treatment, storage, or disposal facilities without obtaining an EPA identification number. Section 66508. This section states that a generator can accumulate hazardous waste for 90 days or less without a permit. Ifa generator plans to store these wastes for more than 90 days, a facility permit has to be obtained unless the Department of Health Services has granted an extention to the 90 day period. Secti on 66723. Total Threshold Limi t-Concentration Values for Persi stant and Bioaccumulative Toxic Substances in Extremely Hazardous Waste are listed in this section. The TTLC limit - as set in this section for arsenic and/or arsenic compounds is 50,000 mg/kg as As. Section 66900. This section lists chemicals names and their concentrations regarded as hazardous wastes or restricted hazardous wastes. Liquid wastes containing chemicals listed in this section at concentrations greater than the specified limits are restricted from land disposal. Arsenic and/or arsenic compounds are included on the list. The limit set Sn this section for arsenic and for arsenic compounds is 500 mg/L. 2844E 75 Section 66905. Land disposal restrictions and schedule for all the chemicals listed in Section 66900 and restricted concentrations are set here. This section also fixes the commencement date for restrictions on land disposal. For arsenic and/or arsenic compounds, land disposal restriction commenced on January 1, 1984. Section 66305. This section fixes the responsibility on the generator to determine if the waste is classified as hazardous or non-hazardous. Section 66471. Hazardous Waste Determination Requirements for Waste Generators are furnished as guidelines to determine if the waste is hazardous or non-hazardous. Sect ion 66744. This section informs the generator of hazardous waste to obtain prior written approval from the Department of Health Services for any waste to be classified as a special waste. Section 6631Q. This section stipulates conditions under which the Department of Health Services can grant a variance from the requirements of hazardous waste management. 2844E 76 Cal iforni a Admi nistrati ve Code Title 23. Subc haDter 15. Discharge of Waste to Land: The sections which apply to disposing of arsenic waste are detailed below. The Regional Water Quality Control Board (RWQCB) has to approve any waste disposal for which the Department of Health Services has issued a variance. The RWQCB has its own standards for classification of wastes. Figure 2.6-1 explains the various classifications, and Figure 2.6-2 explains the criteria adopted for the different classifications. (30) The classifications of RWQCB are in reference to the increased hazard or water quality threat posed by the wastes. Section 2521. This section defines the type of wastes that can be treated as hazardous waste and states that such waste should be disposed in a Class I Waste Management Unit. Section 2522. This section defines the type of wastes that can be treated as designated wastes and states that such wastes should be discharged in Waste Management Units Class I and Class I1 if approved by RWQCB for such disposal. Secti on 2523. This section defines the type of waste that can be classified as non-hazardous wastes. 2.6.1 REDUCTION OF VOLUMES OF ARSENIC WASTE GENERATED STATEWIDE Because filtration is a physical separation process, its application to any wastewater stream where arsenic is in solid form can be considered possible. Only when a detailed process wastewater chemical characterization has been completed as has been done for HP's San Jose facility, can an evaluation be begun of which arsenic removal process is best. 2844E 77 FIGURE 2.6-1 WASTE AND UNIT CLASSIFICATIONS USED IN CALIFORNIA WASTE CLASSIFICATIONS WASTE HEALTH WATER MANAGMENT SERVICES BOARDS UNITS RESTRICTED RESTRICTED NO LAND HAZARDOUS HAZARDOUS DISPOSAL HAZARDOUS HAZARDOUS CLASS I K 0 0 a GIVEN a VARIANCE DESIGNATED CLASS II aN I c!J c!J -z NON- v)a HAZARDOUS CLASS 111 W NOT SOLID a HAZARDOUS 0 zI INERT UNCLASSIFIED (SOURCE: REFERENCE 2) FIGURE 2.6-2 RELA TIONSHIP B€TWEEN WASTE CLASSIFICATION AND CONCENTRATIONS OF TOXIC CONSTITUENTS WASTE CONCENTRATION OF REGULATORY CLASSIFICATIONS TOXIC CONSTITUENTS BOUNDARIES HIGH RESTRICTED HAZARDOUS LEVELS TITLE 22 HAZARDOUS SUBCHAPTER 15 - HAZARDOUS +yes MUST BE MANAGED AS HAZARDOUS? + No HAZARDOUS LEVELS (STLCs,TTLCs) DESIGNATED LEVELS t Yes DEGRADABLE MATER IAL? + No INERT LOW If the arsenic-laden hazardous waste generated in HP's HF Treatment System (treatment of hydrofluoric acid) 1s a common method of treatment for other GaAs microchip manufacturer's process wastewater, then it could be projected that filtration of solid GaAs would greatly reduce this type of waste throughout the state. 2.6.2 ACCEPTABILITY BY INDUSTRY Although acceptability of filtration for arsenic wastewater treatment cannot be directly assessed without chemical characterization data from other manufacturers in the microelectronics industry, it can be said that if such arsenic wastewater has substantial amounts of solid arsenic compounds present, filtration usually presents the most economic and simple process for such wastewater cleanup. 2.6.3 TRANSFERABILITY TO OTHER INDUSTRIES It appears that the transferability of filtration as a cleanup technique for wastewater streams with hazardous solids present is as easily carried out for other industries as it can be for the microelectronics industry. This technique is not new for solid-liquid separation and is already widely used in all manner of processes in all industries. Transferabi 1i ty, therefore, depends on the identified need for such a separation process. be it based on an economic basis a an environmental one. Again, only when a chemical characterization has been completed for each manufacturer's facility can application of filtrat on as a liquidlsolid separation process be prudently considered. 2844E 78 REFERENCES 1. Sisler, et al. 1963. Collese c hemistrv - A svstematic BDD roach. Second edition. Published by Macmillan Company, New York. 2. Cotton, F.A. and G. Wilkinson. 1966 Advanced Inorsanic Chemistrv Second edition. Published by Interscience Publishers, New York. 3. Frey, P.R. 1961. Colleqe Chemistrv - Second Edition. Published by Prentice Hall Englewood Cliffs, New Jersey. 4. 1980 Document of the Threshold Limit Values Fourth Edition. Pub1 ished American Conference by Governmental Industry Hygi eni st, Inc., Cincinnati , Ohio. 5. Cherinksi, S. N. and F. I. Ginzburg, Purification of arsenious waste waters, 1970. Water Pollution Abstract, 14:315-316, 1941. 6. Anonymous. 1970 The economics of clean water. Vol . 111. Inoruanic Chemicals Industrv Profile, U. S. Dept. of Interior, Washington, D.C. 7. Swain, R. E. 1939 waste problems in the nonferrous smelting industry, Industrial Enaineerina Chemistry, 31 :1358-1361, 1939. 8. Stooff, H. and L. W. Haase. 1938 Occurrence and removal of arsenic in drinking waters. Chemical Abstract, 32:6370 (4). 9. Nelles, R. A. and F. D. Amato, 1950 Treatment of arsenical waters with lime. Water Pollution Abstract, 23:125, 1950. 10. Viniegra, G. and R. E. Marquez. 1965 Chronic arsenic poisoning in the Lake Region: Section 4. Treatment of Drinking Water. Water Pollution Abstract, 38:430-431, 1965. R- 1 11. Shen, Y. S. and C. S. Chen. 1964. Relation between black-foot disease and the pollution of drinking water by arsenic in Taiwan. In Proceedings from the Seco nd International Conference Water Pollution Research. Tokvg, 1-173-190, Pergamon Press, New York. 12. Bellock, E. 1972. Arsenic Removal from Potable Water. Journal American Water Works Association, 63:454-458. 13. Curry, N. A. 1972. Philosophy and methodology of metallic waste treatment, presented at 27th Purdue Industrial Waste Conference, Purdue University. 14. Maruyama, T., S. A. Hannah and J. M Cohen. 1972. Removal of heavy metal s by physical and chemical treatment processes. Presented at 45th Annual Conference, Water Pollution Control Federation, Atlanta, Georgia. 15. Electrolytic Metal Corp. 1960. Recovery of Manganese from Solutions Containing Iron, Manganese, Nickel , and Cobalt - Patent, Chemical Abstract, 54: 12960 (c>. 16. Magnusen, L. M., T. C. Waugh, 0. K. Galle and J. Bredfeldt. 1970. Arsenic in detergents: Possible danger and pollution hazard. Science 168 :389-390. 17. Sigworth, E. A. and S. B. Smith. 1972. Adsorption of Inorganic Compounds by Activated Carbon, Journal American Water Works Association, 64:386-391. 18. Buswell, A. M., R. C. Gore, H. E. Hudson, H. C. Wiese, and T. E. Larson. 1943. War problems in analysis and treatment, Journal American Water Works Association, 35:1303-1311. 19. Berezman, R. I. 1965. Removal of inorganic arsenic from drinking water under field conditions. Water Pollution Abstract, 29:185. R-2 20. Nilsson, R. 1971. Removal of metals by chemical treatment of municipal waste water. Water Research, 5:51-60. 21. Dorr-Oliver, Inc. 1968. Cost o f waste water treatment Drocesses, Robert A. Taft Water Research Center Report, No. TWRC-6, U. S. Department of Interior, Washington. D.C. 22. Lund, H. F. 1971. Industrial Pollution Control Handbook. McGraw Hill Book Co., New York. 23. Sotoharu Goto. Filter for removal of heavy metals. Translated from Japanese Kokai Patent Publication No. Sho 56-53741 91981). 24. U. S. Department of Commerce. 1984. National Technical Information Source. Health Assessment Document for Inorganic Arsenic Final Report. PB84-190891. 25. Bhattacharyya, D. et al. 1981. Precipitation of heavy metals with Sodium Sulfide: bench-scale and full-scale experimental results. AIChE Symposium Service, 7209 V.77 Water. 26. Doyle, Richard D. 1979. Use of an extruder evaporator to stabilize and solidify hazardous wastes. Proceedings Mid Atlantic Industrial Waste Conference Pennsylvania, pp. 56-62. 27. Huang, C. P. and P. L. K. Fu. 1984. Treatment of arsenic (VI containing water by the activated carbon process. Jou rnal Water Pollution Control Federation, V. 56, pl-1, N3, pp. 233-242. 28. Gupta, K. S. and K. Y. Chen. 1978. Arsenic removal by adsorption. Journal Water Pollution Control Federations, March, pp. 493-505. 29. Clifford, D. 1982. Processes for removal or inorganic contaminants from water. Water Enaineerina and Manaaement Reference Handbook, pp. 31-38. R- 3 30. Marshack, 3. B. 1985. Waste classification and cleanup level determination guidance document. California Regional Water Quality Control Board, Central Valley Region. 31. Perlmutter, B. A. 1983. Principles of Filtration. Technical Brochure, Pal 1 We1 1 Technology Corporation, WER 5300, February. 32. Perry, R. H. Third Editions, Chemical Engineers Handbook, McGraw-Hi 11, 1973, Sections 16 and 17. 33. Wade, R. et. al. 1981. Semiconductor Industry Study. State of California Department of Industrial Relations, Division of Occupational Safety and Health. 34. Skripach, T. et. al. 1971. Removal of Fluorine and Arsenic from Wastewater of the Rare Earth Industry. Proceeding 5th International Conference Water Pol 1 ution Research 2:III-34. 35. Anonymous. 1986. Filtration and Separation, Special Advertising Section, Chemical Engineering, October 27. R-4 LIST OF INVENTIONS REPORTED AND PUBLICATIONS Envi rosphere and Hew1 ett-Packard compani es in cooperation wi th the Department's A1 ternative Technology and Policy Development Section plan one or more scientific pub1 i cations and/or conference presentations as a result of this project. R-5 CONTRACT DOCUMENT STATE OF CALIFORNIA DEPARTMENT OF HEALTH SERVICES TOXIC SUBSTANCES CONTROL DIVISION ALTERNATIVE TECHNOLOGY AND POLICY DEVELOPMENT SECTION APPLICATION TO STUDY THE REDUCTION OF ARSENIC WASTES IN THE ELECTRONICS INDUSTRY AB685 GRANT PROGRAM April 1986 HEWLETT-PACKARD CO. CONTRACTORS COPY State of Cjitfornla+ealth ana Welfare A9*nCY GRANT AWARD D.Oar?ment of W~JIC~Serrlcei The Department of Health Services hereinafter called the State, hereby makes a grant award of funds to. ~vArn Envirosphere Co., A Divisjon of Ebasco I hereinafter called the Grantee, in the amount and for the purposes and duration set forth in this Grant Award. Proiect Title Grant Number Application to study the reduction of Arsenic waste I in-the electronics industry. From: 6/30/06 rnroupn: 6/30/07 RoIect Director (Namo, aaaress. onone) MS. Gail Brownell, Environmental Engineer State Amount 350/370 West. Trimble Road 24,382 San Jose, CA 95131-1008 -- (408) 435-4183 Lou1 Amount NIJO I FlnJnClJl Officer (Name. J0ar-S. Ohon*) Otnor Amount Mr. Richard L. Jenkins 2,775 Envirosphere Co. A Division of Ebasco - .. 3000 W. MacArthur Blvd. Total RObKt cost Santa Ana, CA 92704 27,778 hereof, the attached two pages, and the herein referenced. exhibits. its acceptance of this grant award and agrees administer the grant project in accordance wlth the terr ThP...- Grantee- - _-- herebv- __, sianifies- to -and condlttons set forth in or Incorporated by reference in this grant award and any applicable statutes or regulatlons of the State STATE OF CALIFORNIA FOR STATE USE ONLY *HEWLETT PACKARD s 24 3s Support General StJtUteS I FI~CJ:vear unencum6erea 8JlJnCe Item ChJ0t.r 0260-001-001(b) 111 1905 185186 AQJ.lncrerrinp Encumarance 1 Function s 1 Consultant and Professional Services *EKVIROSPHERE CO. A~J.oecre~sinp Encumarrnco 1 Line Item Allotment I hereby mrufv upon my own personal knodedgc budgrnd funds 51pnatun of Accountln9 Officer iia 1. TERM -- 2. AMOUNT The amount of this agreement is t 3. EXHIBITS The Grantee agrees to perform all of the work herein specified in this agreement, consisting of two (2) pages subject to and in accordance with all of the terms and conditions set forth in Exhibits A, B, and C, which by reference are hereby made part of this agreement. Exhibit A, Description of Work, consisting of 12 pages. Exhibit B, Department Agreement Terms, consisting Of thirteen pages. Exhibit C, State Additional Provisions, consisting of four pages. All references to "Contractor" and "Contract" shall be interpreted to be "Grantee" and "Agreement", respectively. 4. PROJECT DIRECTOR BcCkwELLis designated the project director on behalf of the Grantee. Any substitution of the project director or other key personnel must be approved by the Department in writing fifteen (15) days before substitution. 5. GRANT MANAGER A - ~fifidflis designated Department grant managei. The Department may char.ge the grant manager by notice given the Grantee at any time. The grant manager's mailing address is Depar ment Gf Health Services, Toxic Substances Control Di-rision, Act: A. %&UAAI , 714/744 P Street, Sacramento, CA 95814. Express or special deliveries shall be addressed to the grant mar.ager at 1219 K Street, Room 132, Sacramento, CA 95814. 6. PAYMENTS Payments to the Grantee under this agreement shall be reimbursement for completion of tasks as specified in Exhibit A. . Progress payments will be made monthly in arrears but not more cften than once a month. All invoices must be submitted with a progress letter. From each invoice, an amount equal to ten percent snall be withheld, pending final completion of the agreement and the Department's approval of the Grantee's performance and work produc:. Payments to be made to Grantee as specified herein shall include all taxes of any description (federal, state, and municipal) assessed against the Grantee by reason of this agreement not to exceed the total amount of this agreement. For the purposes hereof, "progress payment" is defined as incL2dir.g any partial payment of the agreement price during the progress sf the work, even though the work is br2Ken dcwn into clearly identifiable stages Wzeparate tasks. 7. INTERPRETATION To the extent that inconsistencles exist in the interpretatian cf the Gmnt AdAgreement or the exhibits to this agreement, the frJllcIwlng priority of supersession shall prevail: a. Grant Award Agreement terns and conditions; b. Exhibit C: c. Exhibit B: d. Exhibit A. -2- EXHIBIT A DESCRIPTION OF WORK 3.0, SCOPE OF WORK STATEMENT The general approach to performing this study will be to make a broad assessment of the arsenic disposal problem. 3.1 Description of Manufacturina Process A review will be made of how arsenic enters and transits the manufacturing process. The major sources of arsenic addition to the wastes will be identified. These process steps will be examined to prioritize the economic and technical feasibility of removing arsenic. It is very likely that the manufacturing steps will exhibit widely different chemical conditions, hence the capability to remove arsenic may also vary widely. As an example, the use of an anion exchange process to remove arsenate from- the hydrofluric acid solution would not be feasible due to the high concentration' of fluoride which would out compete arsenate for the exchange resin active sites. This same process might be highly effective after neutralization with lime. 3.2 Chemical characterization of Waste Streams Although certain waste streams at HP's San Jose facility have been analyzed previously, a detailed inorganic analysis shogld be performed on the waste from each step in the manufacturing process. At least the constituents shown in Table 3-1 will be determined for each arsenic waste stream. Following the detailed analysis and the determination that the chemical ccmposition is consistent with time, only selected analytes such as arsenic, Ph, fluoride, and calcium will be determined in subsequent work. 3.3 Arsenic CheTistry The objective of this task is to identify those unique aspects of arsenic chemistry which cculd serve as the basis for waste reduction or recycling processes. 3-1 2172E I- -- TABLE 3-1 I CHEMICAL ANALYSIS OF WASTE STREAMS I Constituent Analytical Method I As ICP or AA L Metals Screen ICP I PH Elect rode Fluoride Specific Electrode or I Colorimetry Anion Screen Ion Chromatography I or classical chemistry I I I I I I I I I I 1 2172E I- Arsenic is a member of the nitrogen family of chemical elements (Group 5a of the periodic chart). It is generally considered to be nonmetallic, but it exhibits both metallic and nonmetallic characteristics. The prlnfcpal ores of arsenic are sulfides with oxides and metal arsenides occurring less frequently. Arsenic forms a number of oxides and hydrides. A distinguishing feature of arsenic is the facile thermal decomposition of the hydride (arsine) to yield an arsenic mirror. This feature of arsenic chemistry could be the basis for segregating arsenic into a small volume (see below). Because arsenic, and its compounds, are considered to be highly toxic, the oral, dermal and inhalation toxicity of all expected arsenic forms in the manufacturing steps will be documented using information currently available in standard industrial hygiene reference data. 3.4 Identification of Potential Treatment Processes I In this task, various data bases and scientific literature will be utilized to identify process types which have been used for arsenic waste treatment. I Also in this task, an assessment of other industries using arsenic will be made. These other industries outside of the electronics industry may be able to utilize reclaimed arsenic. , Because arsenic is a chemical element it can not be destructed by conventional treatment processes. Therefore, the number of treatment process types may be rather limited. Examples of possible processes are as follows: o Sulfide Formation Since the most cormon naturally occurring forn of arsenic is as a sulfide ore, fixation of arsenic by sulfide treatment should be investigated. This treatment would have two potential advantages. 3-2 I). 2172E - The arsenic sulfide could be returned to the land. - Or the arsenic sulfide could be recycled to the mining/processing facility which originally produced the arsenic for the electronic industry. o Solidification This process would create a solid mass containing the arsenic waste. The solid product could be disposed to the land if it passed the Resource Recovery and Conservation Act (RCRA) EP Toxicity test and the State of California, Title 22, Waste Extraction Test (WET) procedure. o Ion Exchange This process would transfer arsenic ions from solution onto a solid resin. The spent resin would also need to pass the EP Toxicity and WET procedures. The final volume of the solid may be smaller than that produced by chemical precipation. o Arsenic Generation A somwehat unconventional means of waste disposal would be to convert arsenic to arsine (see chemical equation below). acid As 0 + reducing agent * XY Arsenic treated in this manner would have significant potential to be recycled back to the gallium arsenide manufacturing process. If arsine were thermally decomposed to yield an arsenic mirror, the arsenic would be contained in a very mall volume. 3 -3 2172E 1. . 3.S Evaluation of Treatment Process(es1 3.S.1 Selection Criteria Each potential treatment process, as identified in Task3.4, will be subjected to a selection process which will include at least the following criteria. o Waste Reduction Efficiency - Each process will be Judged based upon its potential to eliminate the greatest quantity of waste from land disposal. o Operational Characteristics The ease of operation, control, and cowntime of the process will be evaluated. o .Health and Safety Because arsenic and its compounds are highly toxic, effective protection for workers will b.2 afforded substantial consideration. The various forms of arsenic and the potential for exposure will be assessed. 0 cost Capital and operation and maintenance (OW) costs will be generally considered. OW costs may involve chemical additives, electricity, maintenance, and personnel (OM). o Effectiveness - If a solid product is produced, it must pass the EP Toxity and California WET procedures. If substantial liquid remains after treatment, it must be sewerable. The Federal Goverment (EPA) has implemented stringent pretreatment standards for the 3-4 2172E I. disposal of wastewater to the sewer. For most cities and counties, the limit for arsenic discharge is less than 1 mg/L. - If recycling/reclamation of arsenic is proposed, the reclaimed product must be acceptable to the industry which receives it. 3.5.2 Recomnended Treatment Technology(ies) The advantages and disadvantages will be discussed in detail for each recormended treatment process. A process flow diagram will be presented for each recomnended treatment process. 3.6 Environmental Perspective This task will involve an assessment of the benefits to the State of California if one or more of the recomnended waste disposal technologies is implemented in the electronics industry. Factors to be considered are as follows : o Reduction of Volumes of Arsenic Waste Generated Statewide An estimate of the current volume of this waste will be made. The impact or percent reduction of this volume will be determined if a treatrnent process is adopted. Transferability of the waste disposal techrcology will be assessed. o Acceptability by Industry Each of the following factors, which will be important to industry will be addressed. - Disposal Costs - Mitigation of Liability - Ease of Implementation - Personnel and Comunity Safety 3-5 2172E 6.0 BUDGET The information on the following pages has been developed based on the scope of work and is presented in a format that complies with the requirements of the Grant Application Manual. Tables 6-1 and 6-2 show the project budget, for the applicant and consultant, respectively. Nature of Proposal This Hewlett-Packard Company proposal constitutes a firm offer to perform the subject work and such offer shall remain firm for a 90-day period commencing April 14, 1986. Direct Salary Rates and Administration The direct salary billing rates are shown below. The direct salary rates include salary, ovemead and allowances for vacation and absences. Employee benefits are at a rate of 12.4%. Personnel Project Director $65.00 Project Manager, Budget Officer $67.27 Senior Environmental Scientist $57.90 Senior Associate Engineer $44.03 Match Share Hewlett-Packett Company will provide all analytical support in the amount of $2,775 for this proposed project. The analysis will be performed by HP's laboratory in Palo Alto, Califomia or a suitably qualified commerical laboratory. 6-1 I. ’ Direct Czcts The direct costs are broken down as follows: Word Processing ($30/hr) $ 800 Auto Travel 200 Travel & Accomnodation 1,237 Report Reproduction & Binding 100 Drafting ($32/hr) 2SO Mail 200 Phone 100 Analytical Services 2,77S , 1 6-2 2172E - TABLE 6-1 DEPARTbENT OF HEALTH SERVICES WASTE REDUCTION GRANT PROGRAM Name of Applicant Hewlette-Packard Company Date Project Title Application to Study the Reduction of Revised Arsenic Waste in the Electronic Industry-AB685 Grant Proqram Project Duration 12 Months Total Match DHS Budaet Share. -Share I. Personnel Services Salaries and Wage $ 650 $ 5 850 Benefits (at Indirect Charges (at W) 1,300 1,300 Total Personnel Services 2.150 2.150 11. Operatinq Expenses Travel Equipment Analytical 2.775 2,775 - Other (Printing, Postage, Phone, etc) Total Operating Expenses 2,775 111. Professional and Consultant Services (Itemize on separate page, $22,232 $22,232 see Table 6-2) 1’4. Construction Expenses (Itemize on separate page) $ - TOTAL BUDGET (I + I1 + I11 + IV) $27.157 $2,775 $21,382 Specify source 21725 TABLE 6-2 EPARTKNT OF HEALTH SERVICES WASTE REDUCTION GfUNT PROGRAM Nane of Consultant Envirosphere Company Date Project Title Application to Study the Reduction of Revised Arsenic Waste in the Electronic Industry-AB685 Grant Promam Project Duration 12 Months Total Match DHS BudQet Share. Share I. Personnel Services Salaries and Wage ' $ 6.802 $ $ 7.646 Benefits (at 12.4%) 644 Indirect Charges (at 153%) 11.698 11,698 Total Personnel Services 19,344 19.344 11. Operatins Expenses Travel $ 1,996 1,996 Equipment Analytical Other (Printing, Postage, Phone, etc) 892 892 Total Operating Expenses 2,888 2,008 111. Professional and Consultant Services (Itemize on separate page, $ f see Table 6-2) IV. Construction Expenses (Itemize on separate page) $ - TOTAL BUDGET (I + I1 + I11 + IV> $22,232 $- $22,237 Specify source 2172E Figure 4-1 DEPARTMENT OF HEALTH SERVICES WASTE REDUCTION GRANT PROGRAM LWORK --- SCHEDULE- Name of Applicant: HE WLETT-PACKARD COMPANY Project Title: APPLICATION TO STUDY THE REDUCTION OF ARSENIC WASTE IN THE ELECTRONICS INDUSTRY - AB 685 GRANT PROGRAM STAFF MONTHS TASK PERSON - -r - MONTHS 1 2 3 4 5 6 7 0 9 10 11 12 1 PROGRESS REPORTS A A a A A A A A A A MEETINGS 1 0 0 0 OTHER REPORTS 0 0 0 0 0 V v 3.1 0.2 .L 3.2 0.2 - 3.3 0.3 - 3.4 0.6 0 0 3.5 0.5 0 0 3.6 0.3 - MANAGEMENT AND 0.3 W 1 ADMINISTRATION I 1 TOTAL 2.4 I I I 1 1 1 I I I I A MONTHL I PROGRESS REPORTS 0 INTERIM REPORT V FINAL REPORT TABLE 5-1 DEPARTENT OF HEALTH SERVICES WASTE REDUCTION (;RANT PROGRAM PRODUCT DESCRITPION Name of Applicant Hewlette-Packard Company Date Project Title Application to Study the Reduction of Arsenic Waste in the Electronics Industry - AB 685 Grant Proqram & TASKS PRODUCT 3.1 Interim-Report Task 3.1 3.2 Interim-Report Task 3.2 3.3 Interim-Report Task 3.3 3.4 Interim-Report Task 3.4 3.5 Interim-Report Task 3.5 3.6 Interim-Report Task 3.6 Draft Final Report Final Report 10 Monthly Progress Reports. ~ ~~~~~ Interim Task Reports may take the place of monthly reports if the time of delivery coincides and the subject material is similar. 2172E -. . ..._ --- . . . . *. TITLE8 GENERAL INDU!XRY SAFXlY ORDERS 0 5214 (RWi8t.f 83, No. 1M) (p. 442.6.85) 1.1. ( . .. . Third Phase: The worker complains of symptoms of peripheral neuritis, ini- ,. tidy of hands and feet, which is essentiall sensory. In more severe cases, motor paralyses occur; the first muscles affectecr are usually the toe extensors and the peronei. In only the most severe caxs will paralysis of flexor mdesof the feet or of the extensor muscles of hands occur. Liver damage from chronic arsenical poisoning is still debated, and as yet the question is unanswered. In cases of chronic and acute arsenical poisoning, toxic effects to the myocardium have been reported based on EKG changes. These findings, however, are now largely discounted and the EKG c es are as- . -_ cribed to electrolyte disturbances concomitant with arsenicalism.% alation of arsenic trioxide and other inorganic arsenical dusts does not give rise to radio- logical evidence or pneumoconiosis. Arsenic does have a depressant effect upon the bone marrow, with disturbances of both erythropoiesis and myelopoiesis. Bibliography Dinman, B. D. 1960. Arsenic; chronic human intoxication.j: Omup. M'. 2 137. t Elkins, H. B. 1959. The Chemistry of Industrial Toxicology, 2nd ed., John Wiley and Sons, New York. - Holmquist, L. 1951. Occupational arsenical dermatitis; as study among employees at a copper-ore smelting works including investigations of skin . reactions to contact with arsenic compounds.Acta. Dem. Venerd. (Supp. 26) 31.1. Pinto, S. S., and C. M.McGill. 1953. Arsenic trioxide exposure in industry. Ind. Med. sur, 22.- 281. Pinto, S. S., and K. W. Nelson. 1976. Arsenic toxicology and industrial e owe. Annu. Rev. Pbannacol. To.u*d16- 95. Take, B. L., D. D.Ulmer, and W.E. C. Wacker. 1964). Arsenic toxicology and biochemistry. AMA Arch. hd&. He& 21: 132. 111. SPUTUM CYTOLOGY Sputum can be collected by aerosol inhalation during the medical exam or . by ntaneous early morning cough at home. Sputum is induced by transoral stionof an aerosolized solution of eight per cent 8 percent) sodium chloride in water. After inhaling as few as three to five breaths the subject usually yields an adequate sputum. All sputum should be collected directly into sixty percent (60 percent) alcohol. Scientific evidence suggest that chest X-rays and sputum cytology should be used together as screening tests for lung tests for lung cancer in h& risk populations such as workers exposed to inorganic arsenic. The tests are to be performed every six months on workers who are 45 years of age or older or have worked in the regulated area for 10 or more ears. Since the tests seem to be complementary, it may be advantageous to 811ternate the test rocedures. For instance, chest X-rays could be obtained in June and Decem ge r and sputum cytologies could be obtained in March and September. Facilities for providing i 1 . TABLE CONTENTS EXHIBIT B: DEPARTMENT AGREEMENT TERMS ...... 1 A . DEFINITIONS . f ...... 1 3. ENTIRE AGREEMENT ...... 1 C . SERVICES AND AGREEMENT ...... 1 D . RELATIONSHIP OF THE PARTIES ...... 2 E . ASSIGNMENT ...... 2 F . REPORTING ...... 2 1 . Monthly Progress Reports ...... 2 2 . Final Report ...... 3 3 . Report Format ...... 4 G . OWNERSHIP OF DRAWINGS. PLANS. AND SPECIFICATIONS ...... 6 H . DISCHARGE OF GRANT OBLiGATIONS ...... 7 I . INVOICE PREPARATION GUIDELINES ...... 7 J . TRADE SECRETS ...... 8 K . PUBLICITY AND ACKNOWLEDGMENT ...... 9 L . PROVISIONS RELATING TO DATA ...... 9 M . APPROVAL OF DELIVERABLES ...... 10 N . NOTICE ...... 10 0 . MODIfICATIONS/CHANGES ...... 13 P . STOPWORKKOTICE ...... 1 .. Q . TERMINATION ...... 19 R . REMEDIES ...... 11 S . SEVERABILITY ...... 11 T . FORCEMAJEURE ...... ;i U . WAIVER ...... 11 V . WORKERS' COMPENSATION ...... 11 W . NONDISCRIMINATION CLAUSE (OCP-1) ...... 11 X . CAPTIONS ...... 12 Y. AGREEMENT IS COMPLETE ...... 13 2. LAWGOVERNING ...... 13 EXHIBIT E DEPARTMENT AGREEMENT TERPS These terms are standard terms to be inciuded as part of the agreement and are not subject to modification or deletion except as provided in Article 0, Modifications/Changes. DEFINITIONS In interpreting this agreement, the following terms shall ha*ie c5e meanings given to these below. Definitions not given below shall be as cited in Title 22, Sections 66CCO through 66230 of the Caiifzrnia Administrative Code (CAC) and Chapter 6.5, Article 2 of the Health and Safety (HbS) Code. 1. "Department" means the Depaztmezt of Health Services. 2. "Crantee" shall mean recipient of funds pursuant to this agreement. 3. "Project director" means that person designated to serve on behalf of the Grantee as official contact and is gi-ien responsibilities for implementing and executing the terms of this agreement. 4. "Grant manager" means the Department staff person who has been assigned the official duty and responsibilities of implementing and executing the terms of this agreement on behalf of the Department and the State. 5. "State" shall mean the State of California, including but not limited to, the Department of Health Services (DHS). 6. "Written change order" shall mean a notice issued by the project manager for nonsubstant ive changes in the kur&Yof Work or the compensation schedule. A written change order will require an amendment to the grant agreement. 7. "!-?ilestone" shall mean a specific e*ier.t defined in tne Description of Work where authorization to prcceea is requirej. --B. ENTIRE AGREEMENT This agreement supersedes all prior agreements, oral or written, Fade with respect to the subject hereof and, tcgether with the Grant Axard Agreement terms and conditions and the exhibits hereto, contains the entire agreements of the parties. c. SERVZCSS AND- AGREEMENT The Grantee shall undertake and perform the services as set forth in the Description of Work, Exhibit A. -1- -D. RELATIONSHIP 02 THE PARTIES The Grantee shall be entitled to make use of its own staff and silch subcontractors as are mutually acceptable to the Grantee and the State. All subcontractors specifically identified in the Description of Xork are considered to be acceptable to the State. Any change in subcontractors shall require a written change order. The Grantee shall be responsible for the work of subcontractcrs, including but not limited to, mcnitoring of task performance: and initiating action t? expedite completion, to maintain the work 3n schedule, or to adjust the schedule to compensate for unavoidable delays. -E. ASSIGNMENT Grantee may not transfer by assignment, subcontract, or novation the performance of this agreement or any part thereof except wich the prior written approval of Department as to each such assignment. The Department's consent to one or more assignments or subcontracts hereunder shall not constitute a waiver or diminution of Department's absolute right to approve of each and every subsequent assignment or subcontract. Grantee may not without prior written approval of the Department assign any other right that he may from time to time have under this agreement. -F. REPORTING -1. Monthly Progress Reports Except as otherwise specified by the State, Grantee shall provide a progress report in writing at least once a month to the grant manager. Each progress report shall include, but not be limited to, a statement that the Grantee is or is nat on schedule, and any pertinent reports to interim findings. Grantee should discuss any difficulties or special problems so that remedies can be developed as soon as p..sible. Grantee shall provide five (5) copies of the report by the tenth of the month foliowing t2e month reported. The mcnthly progress reports shall cDntain the following elements : a. Technical Progress The Grantee's technical report shall include the foliowing: (1) Detailed wcrk plan, including identificaticn of activity and time schedule. (2) Status of tasks and progress to date with percent of completion. -2- (3) Difficulties encountered during the reporting perizd. (4) Actions being taken to rectify problems. (5) Activities planned for the next month. --(6) Changes in personnel. The technical report shall list target and actual completion dates for each activity, including project completion and provide an explanation of d deviation from the miiestones in the schedule. Significant difficulties encountered during the c3urse ,sf the investigation shall be reported immediately t3 the Department's grant manager. b. Financial Management The financial report shall include the following: (1) Actual expenditures, including fee and direct laoor hours expended for period. (2) Cumulative expenditures, including fee and cumulative direct labor hours. (3) Projection of expenditures for completing the project, including an explanation of any significant variation - from the planned expenditures. (4) A graphic representation of planned v. actual expenditures plus fee and comparison of actual v. planned direct labor hours. A projection of costs through completion is to be made for both. --2. Final Report The Grantee shall provide eight (8) copies of a draft verslon of the final report no later than sixty (63) days pricr to the expiration date of this agreement. Review cmments snail be prepared and transmitted by the Department to the Grantee %:thin thirty (30) days of receipt of the draft versicn of tr.e final report. The Grantee shall provide one (1) camera-ready copy plus eight (8) copies of the final report in a form approved by the Department after incorporation of revisions of state-submitted comments. The final report shall be comprehensive and stall report on all work performed and data collected during each phase or task of the project. In the event that this agreement should terminate before a:l work, as specified in the Description of Work, is completed the Grantee agrees, notwithstanding any other clauses or provisions -3- of this agreement, to submit a xritten report to tne Departzent which shall describe all work performed by the Grancee to date.c,f termination. This report shall be done at no additional expense to the Department. -3. Report-- Format All reports and surr,maries, with the exception of the mc!?thly report, plans, and as-built drawings, shall be prepared in the following manner: Each page of the report must be legible and suitabie for photographic reprod!Jction. llse single or one and cne-naif (1 1/2) spacir.g. Do not double or triple space. All pages shail be standard size (8 1/2" x 11") and except for the title page shall be numbered consecutively. Photographic reduction is not acceptable for large tables or figures: these should be presented on consecutive 8 1/2 by 11 inch pages, each page containicg one (1) portion of the large chart. Color presentations are not acceptable: printing shall be black only. Format details are as follows: a. Cover Page b. Title Page c. Abstract The abstract shall indicate the purpose and scope of the work undertaken, the work performed, results obtained, and conclusions. The purpose of the abstract is to provide the reader wit: useful information and with a means of determining *nether the cDmplete document should be obtained for study. Because of the subsequent processing of abstracts for bib1iog:aphic pu:pose, avJoid usage of non-English or special characters and inferior or superior figures (subscripts, fIrmulas, et:.). The lenqth c.5 tke abstract should be about 230 words. d. Acknowledgments Only this section shall contain acknowledgmects cf key personnel and DrganizatiDns who were associated with tr.e project. The last paragraph shall be as fcllows: " Th i s report was submitted in fulfillment of (gi*Je the A9reener.t No.) by (Grantee organization) under the sponsorship of tke Department. Work was completed as of (date)." e. Disclaimer The following statement is to appear near the front of the report: I: "The statements and conclusions of this report are those of the Grantee and not necessarily those of the State of California. The mention of corrimercial prGduCts, their source, or their use in connection with material reported herein is not to be construed as either an actual or implied endorsement of such products." \ f. Table of Contents g. List of Figures This is an cptional item where there are fewer than Ei-Je (5) illustratians. h. List of Tables This is an optional item where there are fewer than five (5) tables. i. Summary and Conclusions Probably the most important part of the report. This section should begin with the statement of what was done and why, and how it was done. Major results of the study should then be presented using clear, concise statements. A simple table or graph may be used also. Finally, conclusions should be presented using clear, concise statements. Often it is useful to itemize major results and conclusions. j. Recommendations Use clear, concise statements to state recommended future action and further study that may be required. k. Body of Report (1) Introduction The scope and purpose of the pr3]ect, cer.eral background of the project, descr:ption of the var;aus phases of the project, theoretical appreach t3 tne solution of the problem being addressed and limitaticfis to the work sha:l be presented in the intraductlor.. (2) Discussions A detailed description and analysis of the work performed during the course cf tP.e project that lead t,3 the conclusions shall be presented. Identification cf innovations or development of new techniques cr processes should be included. Where apprspriate, discussion of cost projections and economic ar.alljsis should appear here. -5- I- 1. References Use consistent references which aze full citations c3 wc:k referenced throuahout the report and references to c:,;sely related work, background materials, and publications i;hich offer additional information on aspects of the wcrk. An --option of the author is to list these at the end of the chapter with citation, or list together in a separate section following the body of the report. m. List of Inventions Reported and Pablications If any inventions have been reported, or publicati2r.s or pending publications have been produced as a result r,f the project, the title, aiJthor, journals or magazines, ar.d identifying numbers wnich will assist in locating such information should be included in this section. n. Glossary of Terms, Abbreviations, and Symbols When more than five (5) of these terms are used in the text of the report, prepare a listing of all with explanations and definitions. It is expected that every abbreviation and symbol will always be defined on its first appearance in the report with a parenthesized symbol. The total count of employed syrbols and abbreviations in the report text does not consider entries in tables or callouts and legends in figures which should be self-contained. 5 OWNERSHIP DRAXINGS, --PLANS, AN3 SPECIFICATIONS The State shall have the right to authorize others to use or reproduce such originals and copies in any manner it (tr.e State) shall deem appropriate. Subject to the conditions as follows: 1. The Department shall have separate and independent ownership of all drawings, design plans, specificaticns, notsbooks, tracings, phctagraphs, negatives, reports, findings, recoymendatiors, data, ar.d memoranda cf every description or any pa:t :hereof, prepazed Lnder this aqreement, and the originals and all copies thereof shall be delivered to the Departnent upo:, request. The Department shall have the full right to USE said originals ar.d copies in any manner when and where it may determine without any claim on the part of the Grantee, its vendors, or suScontract2rs to additional compensation. 2. The Grantee shall retain all proprietary rights, title, 3r.d interest in and to each invention, disczvery, process, or de-zice conceived of cr first reduced to practice by its research and developmental efforts in the course of or under the Grant Award, including the right to develop, produce, market, and otherwise commercially exploit such process or device. The Grantee snall undertake at its own expense to app!y for and acquire such -6- patents as may be available to protect its prcpriecary interests in such process or device. The Grantee will agree to pay to the Department, begir.ning 18 months after the date of the grant, an amount equal tz ten percent of net profits thereafter received from the commercial use or licensing of the process or device, up to a maximum equal ta the total amcunt of the grant, together with interest thezecn accruing from and after the date of the grant at the then prevailing prime commercial lending rate, until tne total amount of the grant with interest is repaid in full. The Grantee will also agree to matce the process or de-iice available to the Department, upon reasonable terms and c3nditi;ns to be mutually agreed upon, for its use for demonstratiDn 3r other departmental purposes, and will at all times use its best efforts to make the process or device available to service such work projects submitted by other nongovernmental applicants as may be referred to it by the Department, upon agreement terms and conditions at least as favorable as those which may from time t3 time be offered to other commercial users, licensees, 3r customers of the Grantee. -H. DISCHARGE 02 GRANT OBLIGATIONS The Grantee's obligations under this agreement shall be deemed discharged only upon submission of an acceptable final report to the State as provided in Article F, Reporting. -I. INVOICE PREPARATION GZIDELINES Requests for payment are to be submitted with an invoice at thccnd ob Uch rnonth'r epfort. Procedures for completing this request are to be as follows: 1. Submitted in quadruplicate with an original signature on at least one copy. 2. S:gned by the person who signed the agreement or hisrher designee. If there is a question as to the authcrity 3f the sigr.er which cannot be resolved to the satisfacticr. of the State, the invoice will not be paid. 3. Invoices mas: identify the agreement by number and 3~s:De itemized in accaraance with the budget pcrtion of Exhlblt A. -7- 4. Mail the payment request to the following address: Department of Health Services Toxic Substances Control Division rl Hazardous Waste Management Section adh- Att: Laura Kaweski *d A% \ Contracts and Records Unit 744 P Street, 308 A(4- ~ACJ~W Sacramento, CA 95814 Grantee Name: Agreement No.: --J. TRADE SECRETS 1. The Grantee and the Department understand that each party may come to possession of information and/or data which may be deened confidential or proprietary by the person or organization furnishing the information or data. Such information or data, whether in any form of electronic, mechanical, or other recording, in the possession of the State may be subject to disclosure under the California Public Records Act, commencing with Government Code, Section 6250. The Department agrees not to disclose such information or data furnished by the Grantee and to maintain such information or data as confidential, when SO . designated by the Grantee in writing indicating the material to be trade secrets at the time it is furnished to the Department, only to the extent that such information or data is exempt from disclosure under the California Public Records Act. No obligations of the parties with respect to such confidential and proprietary information will terminate after any date an which: a. Such information appears in issued patents or printed publications or is shown to be in public domain for reas3ns other than breach of this agreement; or b. The party receiving such informtion can shcw by written records that such information was in its possessizn prior to acquiring such information from the cther party or that such information was independently devel2ped by its enployees whs did not have knowledge of such informatian. 2. "Trade secret" as defined in Section 25173 of the HhS Code, is such data as the Grantee has identified in a satisfactory manner as being under Grantee's control prior to commencemest of performance of this agreement, and which the Grantee has reasonably demonstrated as being of a proprietary nature either by reason of copyright, patent, or trade secret doctrines in full force and effect at the time when performance of this agreement is commenced. The title "trade secrets" shall remain with the Grar.tee throughout the term of this agreement and thereafter. As to "trade secret" the extent of Department access to the same and -8- the testimony available regarding the same shall be limited :3 that reasonably necessary to demonstrate, in a scientific Iliazcer to the satisfaction of scientific persons, the validity of any premise, postulate, or conclusion referred to or expressed in any deliverable hereunder. -K. PUBLICITLAND- ACKNOdLEDGMENT 1. The Grantee agrees that it will acknowledge the Department support whenever projects fur,ded, in whole or in part, by this agreement are publicized subject to restricticns of this agreement in any news media. 2. The Grantee will r,ct issue any press release or make avai1aG:e (except to the Departmect) any reports, information, inventions, improvemerts, discoveries or data obtained, prepared, assembled, or developed by the Grantee pursuant to this agreement, without prior written app:oval of the Department while the agreement is in force. The 3epartment's approval shall not be unreasonably withheld. -L. PROVISIONS RELATING DATA 1. "Generated data" is that data which the Grantee has collected, collated, recorded, deduced, readout, or postulated for utilization in the performance of this agreement. Any electronic data processing program, model, or software system developed or substcntially modified by the Grantee in the performance of this agreement at state expense, together with complete documentation thereof, shall be treated hereunder in the same manner as "generated data". "Generated data" shall be the property of the Department unless and only to the extent that it is specifically provided otherwise herein. 2. "Deliverable data" is that data which under the terms Of tkis agreernent is required to be delivered to the Department and shall beiong -to the State. 3. P.s t3 "generated data" shich is reserved ta Grantee t.;. :ks express terms herein and as to any preexisting 3r "propriera:y data" (Article J., Trade Secrets, part 2) which has been utii::ei to support any premise, postulate, or conclllsilsn refecred :a cr expressed in any deliverable hereunder, Grantee snal? preser-;e the same in a fcrm which may be introduced as evidence in a ccii:~ of law at Grantee's own expense for a pericd of not less tt,an three years after receipt by the Department of the final repcrt herein. 4. PriQr to the expiration of such time and before changing the fc:~ of or destroying any such data, Grantee shall notify tF.e Department of any such contemplated action and the Department may, within thirty (30) days after said notification, determine whether it desires said data to be further preserved. If t3e Department so elects, the expense of further preserving said data shall be paid for by the Department. The Grantee agrees that the -9- Department may at its own expense hasle reasonable access t3 caij data throughout the time during which said data is preser.fcd. Grantee agrees to use his best efforts tC) furnish cmpete.r,t witnesses OK to identify such competent witr.esses t3 testif;. ir. any court of law regarding said data. M- APPROVAL 42 DELIVERABLES Each deliverable to be provided under this agreement shall be apprc:.ed by the grant manager. --N. NOTICE Notice to either party may be given by certified mail properly addressed, postage fully prepaid, to tne address beneath the came of each respective party. Such notice shall be effective when recei-red, as indicated by post office recDrds, c)r if deemed undeliverabie by post office, such notice shail be effective nevertheless fifteen (15) days after mailing. Alternatively, notice may be given by personal delivery to the party at the address designated. Such notice shall be deemed effective when delivered unless a legal holiday for state offices commences during said 24-hour period, in which case, the effective time of the notice shall be postponed 24 hour for each such intervening day. For the above purposes, the Department's name and address are the name and address of the grant manager. -0. MOD-IFICATIONS/CHANCES Any change to this agreement shall require a written change order and an agreement amendment. If this agreement was subject to the approval of the Department f General Services, then there must also be such approval fo: a modification or amendment thereto, with the following exception: An amendment to the agreement which only extends the original time for completion of performance for a period of one (1) year cr less is exempt from the Department of Ger.eral Ser-iices. The agreement may only be amended once under this exempticn. -P. ---STOP WORK NOTICE Immediately upon receiving a written r.c,tice t3 stor, wzrk, the Grazcee shall cease all WO~Kunder this agreement. QL QL TERMINATION The Department shall have the right tz terminate this ag:eenent at its sole discretion at any time upon thirty (30) days written not:ce t3 the Grantee. In the case of early termination, a final paymerit will be made to the Grantee upon receipt of a report and invoice covering costs incurred prior to terminati3n. The total of all payments, including the final payment, shall not exceed ninety (90) percect of the amount of this agreement. -10- -R. REMEDIES Unless otherwise expressly provided herein, the rights and remedies hereunder are in additiGn to, and not in limitation of, other riqhts and remedies under the agreement, at law or in equity, and exercise the one (1) righ: cr remedy will not be deemed a waiver of any other right or Ssmed:;. -S. SEVERABILITY Any provisions here>: prc3ibited by or unlawful or unenforceable ur.der any applicable law of ar,y jurisdiction shall, as to such jurisdiction, be ineffective 'xith!?i;t affecting any other provision of the agreemert. To the full extent, however, that the prcvisions of such applicable law may be vaived, they are hereby waived, to the end that the agreement be deemed to be valid and bindir,g. Tr FORCE MA J E'JR E Neither the State nor the Grantee, including the Grantee's subcontractirs, if any, shall be responsible hereunder for any delay, default, or nonperformance of this agreement, other than the payment of monies due hereunder, to the extent that such delay, default, Or nonperformance is caused by an act of God, weather, accident, labor strike, fire, explcJsion, riot, war, rebellion, sabotage, flood, epidemic, act of government authority in either its sovereign OK contractual capacity, Labor, material, equipment or supply shortage, or any other cause beyond the reasonable control of such party. --U. WAIVER No waiver of any breach of this agreement shall be held to be a waiver of any other or subsequent breach. All remedies afforded in this agreement shall be taken and construed as cumulative, that is, in addition to every other remedy provided therein or by law. The failure of the Department to enforce at any time any of the provisions of this agreement, or to require at any time performance by Grantee of any of the provisions, therefore, shall in no way be constraed ta be a waiver of sach provisions nor in any way affect the validity of tnis ag:ee!rent 0: any part thereof or the right to State t3 thereafEer efiforce each and every such provisign. -V, WORKERS' C0MTENSAT:ON Grantee hereby warrants that it carries Workers' Compensaticn Insurance fer all of its employees who will be engaged ir. the performance ~f this agreement and agrees to furnish to the Department satisfactory evidence thereof at any time the Department may request. W. NONDISCRIMINATION CLAUSE (OCP-1) 1. During the performance of this agreement, Grantee ar.d its subcontractors shall nct unlawfully discriminate against any employee or applicant for employment because of race, reliqicn, color, national origin, ancestry, physical handicap, medical -11- E condition, marital status, age (over 30), GK sex. The Gractees and subcontractors shall ensure that the evaluation and treatment of their employees and applicants for employment are free ,of such discrimination. The Grantees and subcontractors shall ccmply with the provisions of the Fair Employment and Housing Act (Government Code, Section 12900, et seq.) and the applicable regdations pronulgated thereunder (CAC, Title 2, Secticn 72850, et seq.). The applicable regulations of the Fair Employment and Housing Comriss:cn implementing Government Code, Section 129313, set fsrth in Chapter 5 of Division 4 of Title 2 of CAC are incorporated intn this agreement by reference and made a part hereof as if set forth in full. The Grantee and its subcontractors shall give written nctice of their obiigations under this clause t3 labcr organizations with which they have a collective bargaining or other agreement *& 2. This Grantee shall include the nondiscrimination and compliance provisions of this clause in all subcontracts to perform under this agreement. 3. The Grantee will permit access to his records of employment, employment advertisements, applicant's forms, and other pertinent data and records to the State Fair Employment and Housing Commission, or any other agency of the State of California designated by the awarding authority, for the purposes of investigation to ascertain compliance with this section. 4. Remedies for Unlawful Practices a. The State may determine unlawful practices, under the Fair Employment Practices section of this agreement, to have occurred upon receipt of a final judgnent having that effect from a court in an action to which the Grantee was a party, or upon receipt of a written notice from the Fair Employment and Housing Commission that it has investigated and determined that the Grantee has violated the employment provisions of the Fair Employment and Housing Act and has issued an order under Government Code, Section 12970, which has become final. b. Fc?r unlawful practices under this Fair Employment Practices provision, the State shall have the right to termirkate this agreement either in whole or in part. Any loss or danage sustained by the State in securing the goods or services hereunder shall be borne and paid for by the Grantee and by this surety under the performance bond, if any. The Stace may deduct, from any moneys due or that may becme due t3 tne Grantee, the differezce between the price narred ;n the agreement and the actual cost thereof to the State. -X. CAPTIONS The clause headings appearing in this agreement ha*Je been inserted fzr the purpose of convenience and ready reference. They do not purport -12- to and shall not be deemed to define, limit, or extend the scr,pe cr intent Of the clauses to which they appertain. -Y. AGREEMENT COMPLETE Other than as specified herein, no document or communication passing between t-e parties hereto shall be deemed a part of this agreenent. -2. GOVERNING Understood and a3:eed that this agreement shall be goverrred by the laws of the State of Califorcia both as to interpretation and perfarnance. hd-ATPD-7-mt -13- I’ Exhibit A (C) EXHIBIT C STATE OF CALIFORNIA DEPARTMENT OF HEALTH SERVICES ADDITIONAL PROVISIONS (Fur Consultant md Personal Services ConPrU) (1) There is no Paragraph (1) in this Exhibit A (C). (2) Trave1 and Pcr Diem Contractor agrm that all travel and per diem paid its employees under this agreement shall be at rates not to exceed those amounts paid to the State’s represented employees under collective bargaining agreements currently in effect, No travel outside the State of California shall be reimbursed unless prior minen authoriz8tion is obtained from the State. (3) Strndvdr of Work The Contractor agrees that the performance of work and services purrurnt to the requirements of this contract shall conform to high professional standards. (4) Ingection The State, through any authorized representatives, has the right at all reasonable times to inspect or otherwise evaluate the work performed or being performed hereunder including subcontract supponed activities and the premises in which it is being performed. If any inspection or evaluation is made by the State of the premises of the Contractor or a subcontractor. the Contractor shall provide and shall require his subcontractors to provide all reasonable facilities and assistance for the safety and convenience of the state representatives in the performance of their duties. All inspections and evaluations shall be performed in such a manner as will not unduly delay the work. (5) Rights in Diu A. Subject Data. As used in this clause, the term “Subject Data” means writings, sound recordings, pictorial reproductions, drawings, designs or graphic representations, procedural manuals, forms, diagrams, workflow charts, equipment descriptions, data files and data processing or computer programs, and works of any similar nature (whether or. not copyrighted or copyrightable) which are first produced or developed under this contract. The term does not include financial reports, cost analyses, and similar information incidental to contracr administration. B. Fccderul Gouetnnrenr ond State Rghrs. Subject only to the provisions of (C) below, the Federal Government and State may use, duplicate, or disclose in any manner and for any purpose whatsoever, and have or permit others to do so. all Subject Data delivered under this contract. i. License io Copyrighted Data. In addition to the Federal Government and State rights as provided tn (5) above, with respect to any subject data which may be copyrighted, the Contractor agrees to and does hereby grant to the Federal Government and State a royalty-free, noncxrlusive and irrevocable license throughout the world to use. duplicate, or dispose of such data in any manner for State or Federal Government purposes and to have or permit others to do so. Provided. however. that such license shall be only to the extent that the Contractor now has. or prior to completion or final settlement of this contract may acquire, the right to grant such license without becoming liable to pay compensation to others solely because of such grant. -1 - CMS Instructional Bullotln No. 05 (3/85) I Exhibit A(C) (9) National kbor Rcktion~Bod Certifiution (Not applicable if Contractor is a public entiry) Contractor. by signing this agreement, does swear under penalty of pcrjury that no more than one final unappedable finding of contempt of COUR by a Federal court has been issued against Contractor within the immediately preceding two-year period because of the Contractor's failure to comply with m order of 8 Federd COUR which orders the Contractor to comply with an order of the National Labor Relations Board. (10) Dacumeno md Written Rcpom Any document or written report prepared as a requirement of this agreement shall contain. in a separate zcction preceding the main body of the document. the number and dollar amounts of all conuacts and subcontracts relating to the preparation of such document or report. if the total cost for work by nonemploym of the State exceeds ss ,OOo. (11) Audits Contractor agrees that this contract, is subject to examination and audit by the State. indudmg the Auditor General, for a period of thmyeus after final payment by the State to Contractor under said contract. (12) Resolution of Contract DisDuag A. If Contractor believer there is a dispute or grievance between Contractor and the State, the following two- step procedure shall be followed by both parties: 1. The Contractor should first discuss the problem informally with the program contract administrator within the Department. If the problem cannot be resolved at this stage, the Contractor must direct the grievance together with any evidence, in writing, to the program section chief. The grievance must state the issues in the dispute. the legal authority or other basis for the Conmctor's position and the remedy sought. The section chief must make a determination on the problem within ten (10) working days after receipt of the written communication from the Contractor. The section chief shall respond in writing to the Contractor indicating the decision and reasons therefor. Should the Contractor disagree with the section chiefs decision, he/she/it may appeal to the second level. 2. Thc Contractor' must prepare a letter indicating why the section chief's decision is unacceptable, attaching to it the Contractor's original statement of the dispute with supporting documents along with a copy of the section chicf's response. This letter shall be sent to the division chief of the division in which the section is organized within ten (10) working days from receipt of the section chief's decision. The division chief or designee shall meet with the Contractor to review the issues raised. A written decision signed by the division chief or designee shall be retumed to the Contractor within twenty (20) working days of receipt of the Contractor's letter. (1 3) Evdu8tion of Consulmt Contractors The Contractor's performance under this contract shall be evaluated at the conclusion of the term of this contract. The evaluation shall include, but not be limited to: A.. Whether the contracted work or services were completed as specified in the contract, and reasons for and amount of any cost overruns. -3 - State of California CALIFORNIA ADMINISTRATIVE CODE TITLE 8. INDUSTRIAL RELATIONS Chapter 4. Division of Industrial Safety (Industrial Safety Orders) 2777E iia $5214 GENERAL INDUSTRY SAFEIT ORDERS TITLE 8 (p. 442.6.66) (Rogirtor 83, No. 1- )( 5214, Inorganic Arsenic. Scope and Application. This section establishes requirements for the control of employee expo- sure to inorganic arsenic. (2) This section applies to the manufacture, reaction, release, packaging, repackaging, stora e, handling, disposal or other use of inorganic arsenic except as otherwise provi9 ed by this subsection. This section a plies to the trans orta- tion of inorganic arsenic except to the extent that the & ornia Highway Katrol ate the hazards covered b this section. section does not apply to x e use of inorganic arsenic registered with Department of Food and Agriculture where such use occurs in: (A) Pesticide application in agriculture, or (B) Distribution, sale and use of mt control devices. (4) This section applies to the manufacture and use of wood preservatives containin inor anic arsenic but does not apply to the utilization of arsenically preserve cfw (5) This sectionJ. does not apply to electronic products or components which contain gallium arsenide in encapsulated form. (6 This section does not apply to the storage, transshipment, distribution, or sale of inorganic arsenic in intact, sealed containers exce t that the require- ments for notification of use and incidents (Section 5214(B )), procedures for the effective cleanu of spills and leaks (Section 5214(j)), and signs and labels (Section 5214(1)) sfd apply (7) The r uirements of this section are subject to the provisions of the Occupational75 arcinogens Control Act of 1976 (Health and Safety Code, Divi- t, sion 20, Chapter 2). b) Definitions. A ction Level. An &hour time-weighted average concentration of 0.005 mil- ligrams of inorganic arsenic (as arsenic) per cubic meter of air. Authorized person. Any employee or other person specifically authorized by the employer, whose duties require access to a regulated area, including any empIoyee or employee representative designated to observe the performance of monitorin and measurin procedures pursuant to Title 8, Section 340.1, California Jmmtrative de. Chief. The Chief of the Division of Occupational Safety and Health, P.O. Box 603, San Francisco, CaIifornia 94101. Director. The Director, National Institute for Occupational Safety and Health, U.S. De arbnent of Health, Education and Welfare, 5600 Fisher Lane, Rockville, Mary Pand 20852. Incident. Any Occurrence such as, but not limited to, equipment failure, ru ture of containers, or failure of control equi ment resulting in the unexpect- e release of inorganic arsenic into an area w K ere employees, unprotected by appropriateB respirators, clothing or equipment in accordance with Sections 5214(h) (2) (A) or 5214(i), are exposed to concentrations in excess of 1.0 milli- grams per cubic meter of air or are subjected to direct skin or eye contact with arsenic trichloride, tibromide, or trifluoride. Inorganic arsenic. Elemental arsenic and all of its inorganic compounds, including copper acetoarsenite (Paris Green),with the exception of arsine. For the purposes and requirements of this section, any substance of a total inorganic arsenic content of 0 02 percent or less, by weight, is excluded from this defini- tion. TITLE 8 GENERAL, INDUSTRY SAFETY ORDERS 0 5214 (Regbter 81, No. 22-1) i (p. 442.6.67) Fit Testing. A rdurewhich tests for leakage at the juncture facepiece ana the wearer's face by determining whether or not agent is detectable by the respirator wearer while exposed to a test atmosphere. Quantitative Fit Testing. A procedure using sophisticated instrumentation which measures the concentration of a test agent inside a respirator while worn in a test atmo here of known concentration; the ratio of the concentration of the a ent in %e test atmosphere to its concentration inside the respirator provi f es a numerical value (the protection factor) indicative of the degree of protection afforded the wearer by the respirator. (c) Permissible Exposure Limit. During a work day, no employee shall be exposed to airborne inorganic arsenic in excess of an &hour time-weighted average concentration of 0.01 milligrams (as arsenic) per cubic meter of air. (d) Reporting of Use and Incidents. (1) Use. Within 60 days of the effective date of this Order, or within 60 days following the introduction of inorganic arsenic into the workplace, the informa- tion rescribed by this paragra h shall be re rted in writing to the Chief. Any ,,$cant chan e in such drmation sh apbe similarly reported within 15 c endar days o such change. (A) The nameB and address of each workplace in which inorganic arsenic is - present. (B) The chemical name (s) or other identifying information as to the pres- ence of inorganic arsenic in the wor ace. (C) Where a regulated area mustkg' e established within the workplace in i accordance with Section 5214(f) (1): 1. An identifying descri tion of the in-plant location(s). 2. A brief description of! each process or operation which creates the em- . .-._. ployee exposure to inorganic arsenic, the a proximate number of employees engaged in each process or operation, an (P the actions which the employer intends to take to reduce exposures. (D) The names and addresses of any collective bargaining units or other representatives of the affected em loyees. (2 Incidents. Any incident sh& be reported in accordance with this para- !Taph * (A) A re ort of the occurrence of the incident and the facts obtainable at that time s all be made within 24 hours to the nearest district office of the Division of KOccupational Safety and Health Administration. (B) A written report shall be filed with the Chief within 15 calendar days thereafter which shall include a description of the operation or process and the in-plant location involved, a statement of the known or estimated extent of employee exposure to inorganic arsenic, an anal sis of the circumstances result- ing in the incident, and a description of remedi Jmeasures taken or to be taken, with specific completion dates, to prevent further similar incidents. A copy of each written report required by this subsection shall be (3)posted in t e location(s) where inorganic arsenic is present in the workplace or in other appropriate location (s) where the posting is conspicuous to affected employees. Each written report shall be posted for a minimum period of 30 days. I I.:.. $5214 GENERAL INDUSTRY SAFETY ORDERS TITLE8 (p. 442.6.68) (Regi8ter 81, Na 22-1) (e) Exposure Monitoring. c (1) General. (A A determination of the concentration of airborne inorganic arsenic to whic b each employee is exposed on an &hour time-wei hted average basis shall be made from air samples that are representative of tI e employee’s exposure without regard to the em loyee’s use of respiratory protective equipment. (B) The em loyer shaf collect full shift (for at least 7 continuous hours) personal samp es including at least one sample for each shift for each job classification inP each work area. (2) Initial Monitoring. Each workplace in which inorganic arsenic is present, including each use, operation or process involving inorganic arsenic, shall be monitored in accordance with Section 5214 (e)(1) within 30 days of the effective date of this Order. (3) Frequency. (A) If the determination conducted pursuant to Section 5214 (e)(2) reveals an employee’s exposure to be in excess of the ermissible exposure limit, moni- c toring shall be repeated at least uarterly un two consecutive measurements, taken at least seven days apart, emonstratetf that such employee’s exposure no longer exceeds the permissible 3limit. (B) Whenever an employee’s exposure is demonstrated to be at the permis- sible exposure limit, or below the permissible exposure limit but at or above the action level, pursuant to determinations conducted in conformance with Sec- tion 5214(e) (2) or (e)(3) (A), monitoring of the employee’s exposure shall be repeated at &month intervals, as a minimum, thereafter. Such measurements shall be continued until two consecutive determinations, taken at least seven days a art, are below the action level and thereafter monitoring may be discon- tinueB except as required by Section 5214 (e) (4). (C) Whenever an employee’s exposure is demonstrated to be below the action level upon initial monitoring, in accordance with Section 5214(e) (2), no further monitoring is required except as required by Section 5214 (e) (4). (4) Additional Monitoring. Whenever there has been a personnel, produc- tion, process, control, or other change which may result in new or increased e owe to inorganic arsenic, additional monitoring which complies with this su section shall be conducted for all potentially affected employees within 30 daysT of any such change. (5) Employee Notification. (A) Within five working days from the receipt of monitoring results, each employee shall be notified in writing of the results which represent that em- ployee’s exposure. (B) Whenever the monitoring results representative of an employee’s e - sure indicate that the employee’s exposure was in excess of the nnissiT le limit, the written notice shall include a statement that the permissibp” e limit was exceeded and shall include a description of the corrective action being taken to reduce the employee’s exposure to or below the permissible exposure limit. (6) Accuracy of Measurement. (A) A method of monitoring and measurement shall be used which has an accuracy (with a confidence level of 95 percent) to within plus or minus 25 percent for concentrations of airborne inorganic arsenic, as arsenic, equal to or greater than the time-weighted average permissible exposure limit. TITLE8 GENERAL INDUSIRY SAFER ORDERS 0 5214 ' (Register 81, No. 22-1) (p. 442.6.69) ( (B) The employer shall use a method of monitoring and measurement which has an accuracy (with a confidence level of 95 percent) of not less than plus or minus 35 percent for concentrations of airborne inorganic arsenic greater than 0.005 milligrams per cubic meter of air but less than 0.01 milligrams per cubic meter of air. Authority cited: Labor Code Section 142.3. Reference: Health and Safety Code 24230. (f) Regulated Areas. (1) Regulated areas shall be established where employee exposures to air- borne inorganic arsenic, without regard to the use of respirators, are in excess of the permissible exposure limit. (2) Regulated areas shall be demarcated and segregated from the rest of the workplace in any manner that "izes the number of persons potentially exposed to inorganic arsenic. The posting of re ated areas shall be in conform- ance with Section 5214(1 (2) (A) of this stanP ard. (3) Access to regulate d areas shall be restricted to authorized persons or to other persons authorized under the provisions of Labor Code Section 6314 (a). (4) AU persons entering a regulated area shall be provided with a respirator selected in accordance with Section 5214 (h). Authority cited: Labor Code Section 142.3. Reference: Health and Safety Code !24230. (g) Compliance. (1) Methods. (A Employee exposure to airborne inorganic arsenic shall be controlled at or be 1ow the permissible limit solely by means of engineering and work practice controls except to the extent that such controls are not feasible. Where engi- ( neering and work exposures to or ' below the used to reduce controls which can be institut- do not reduce and maintain employee exposures to or below the permissible limit, respiratory protective equipment, in conformance with Section 5214 (h),shall be utilized to effectively control exposures within the permissible limit. NOTE: Employee rotation or other administrative controls are not required before respi- ratory protection is instituted. ( (C) Employee rotection against exposure to e e or skin contact with inor- ganic arsenic shall\ e provided by engineering an crwork practice controls and, in accordance with Section 5214 (i) ,by personal protective clothing and equip- ment. (2) Written Program. (A) Within 60 days of the effective date of this section, the employer shall establish and implement a written program to limit exposure to or below the permissible exposure limit by means of engineering and work practice controls. (B) Written plans for these compliance programs shall include at least the following: 1. A description of each operation in which inorganic arsenic is emitted; e.g. machinery used, material processed, controls in place, crew size, operating procedures and maintenance practices; 2. Engineering plans and studies used to detennine methods selected for controlling exposure to inorganic arsenic; 3. A report of the technology considered in meeting the permissible expo- sure limit; 4. Monitoring data; .- -. .. 1. 1 .' . 0 5214 GENERAL INDUSZlRY SAF" ORDERS ' TITLE8 (p. 442.6.70) (Rogi8tor 81, Na 22-6-3041 5. A detailed schedule fbr implementation of the en eering controls andY work practices that cannot be implemented immediateY y and for the adapta- tion and implementation of any additional engineering and work practices necessary to meet the permissible exposure limit; 6. Whenever the employer will not achieve the permissible exposure knit eering controls and work practices by December 31,1979, the em- ployerwith s all include in the com liance plan an anal sis of the effectiveness of the various controls, shall instalfen eering controh and institute work prac- tices on the quickest schedule feasib$" e, and shall include in the compliance Ian and implement a program to "ize the discomfort and maximize the e# ec- tiveness of respirator use; and 7. Other relevant information. (C) The plan r uired by this paragraph shall be revised and updated at least every six mo% to reflect the current status of the program. (D) Written plans required by this paragraph shall be submitted to the Chief upon the request of authorized representatives of the Division of Occu ational(- Safety and Health Administration and shall be available at the workpP ace for examination and copying by such authorized representatives or by any affected em loyee or employee representative. (E) Respiratory Protection. (1) General. (A) Respiratory protective equi ment shall be provided, and the employer shall also require a ropriate empP oyee use to effect compliance with Section 5214(g) 1) (B) anisuring emergencies. (B) e provision and use of respiratory protective equipment shall conform with theA requirements of this subsection and Section 5144. c (C) The employer's obligations pursuant to this subsection commence upon the effective date of this Order for in excess of an &hour time-weighted average inorganic arsenic per cubic meter of air and of this Order for employees exposed in excess of an &hour time-weighted average concentration of 0.01 milligrams of inorganic arsenic per cubic meter of air. (2) Equipment Selection and Use. (A) Appropriate selection, provision, and use of respiratory protective equipment shall be b& on the following table. ( I' ------ TITLE 8 GENERAL INDUSTRY SAFETY ORDERS $5214 (Register 81, No. 22-540-81) (p. 442.6.71) RESPIRATORY PROTECTION FOR INORGANIC ARSENIC CONC" TYON OF AIRBORNE 1NORGWV.C ARSENIC RBPl..TOR TYPE 1. Not greater than 0.1 milligrams (of Air-purifying, with high efficiency par- compounds with no sigruficant vapor ticulate filter+ and half-mask; pressure) per cubic meter Any supplied air respirator with half- mask. 2. Not greater than 0.1 milligrams of See respirator type required under 4. arsenic trichloride (and all compounds with significant vapor pressure) per cubic meter 3. Not greater than 0.5 milligrams (of Air-purifying, with high efficiency par- compounds with no sigmficant vapor ticulate filter and full facepiece; pressure) per cubic meter Any supplied air respirator with full face- piece; Any self-contained breathing apparatus with full facepiece. 4. Not greater than 0.5 milligrams of Gas mask, front or back mounted, arsenic trichloride (and compounds with equipped Hith high efficiency filter*, significant vapor pressure) per cubic acid gas canister, and fdfacepiece; meter Any supplied air respirator with full face- piece; Any self-contained breathing apparatus with full facepiece. 5. Not greater than 10 milligrams (of Powered air-purifying, with high effi- compounds with no significant vapor ciency particulate filter+ and half-mask, pressure) per cubic meter full facepiece, hood, or helmet; Supplied air, operated in positive pres- sure mode, with half-mask. 6. Not greater than 10 milligrams of See respirator type required under 7. arsenic trichloride (and all compounds with significant vapor pressure) per cubic meter 7. Not greater than 20 milligrams per Supplied-air, operated in positive pres- cubic meter sure mode, with full facepiece, hood, hel- met, or suit. 8. Firefighting and/or any unknown, or Self-contained breathing apparatus with known concentration full facepiece operated in pressure-de- mand mode; Combination breathing apparatus: sup- plied-air, positive pressure full facepiece respirator with auxiliary self-contained compressed air supply.' * High efficiency filter-99.97 percent -efficiency -- against.. 0.3 micrometer .. ... I -. 4 5214 GENERAL, INDUSTRY SAFZIY ORDERS TITLE8 .. (p. 442.6.72) (R.giater 81, No. -1) (B) Where emplo ee exposures exceed the rmissible exposure limit for inor anic arsenic an B also exceed the relevant Ktfor particular gases, such as s&ur dioxide, any air purifying respirator supplied to the employee as mitted by this standard must have a combination high efficiency filter witReaf& appropriate gas sorbent. (C) Where air purifying as and vapor cartridge (s) or canisters are used, the cartridge (s) or canisters shafi be re laced nor to the expiration of their service life, or at the completion of each sL,w chever occu~sfirst. A label shall be attached to the cartridge or canister to indicateL the date and time at which it is first installed on the re irator. (D) The employer sh 3perform qualitative fit tests at the time of initial fitting and at least semi-annually thereafter for each employee wearing respira- tors, where quantitative fit tests are not required. (E) Employers with more than 20 employees wearing respirators shall per- form a quantitive face fit test at the time of initial fitting and at least semi- ( annually thereafter for each employee wearing negative pressure respirators. The test shall be used to select facepieces that provide the required protection as prescribed by Section 5214(h) (2) (A). (F) If an employee has demonstrated difficulty in breathing during the fitting test or during use, he or she shall be examined by a qualified physician to determine whether the employee can wear a respirator while performing the required duty. (3) Employee Options. (A) Em loyees who wear respirators shall be allowed to leave work areas to wash the Pace and respirator facepiece as needed to prevent potential skin (, irritation associated with respirator use. (B) Where &-purifying respirators are re uired for protection against inor- ganic arsenic particulate, the employee sh 3 be permitted to change filter elements whenever an increase in breathing resistance is detected, and the employer shall maintain an adequate supply of filter elements for this purpose. (C) Where compliance with this section requires emplo ee use of an air- purifying re irator for a major ortion of the work shift, e employer shall provide, at xe option of each Jected employee and withinx 120 days of the effective date of this Order, a powered respirator. (i) Protective Clothing and Equipment. (1) Provision and Use. Where the probability of skin or eye irritation from inor anic arsenic exists and for all workers working in regulated areas, the empf oyer shall provide at no cost to the em lo ee, and require that employees use appropriate and clean protective work BLgand equipment such as, but not limited to: (A) Coveralls or similar full-body work clothing; (B) Gloves, and shoes or shoe coverlets; (C Face shields or vented goggles, when necessary to prevent eye irritation, whic h comply with the requirements of Article 10; and (D) Impervious clothing for employees subject to exposure to arsenic tri- chloride. (2) Cleaning and Replacement. (A) Protective clothing and equipment shall be cleaned, laundered, re- paired, replaced, or dlsposed of in a manner which complies with all applicable provisions of th$ Order. TITLE 8 GENERAL INDUSTRY SAFETY ORDERS $5214 .. ( (Rogirtsr 81. No. 22-11 (p. 442.6.72.1) (B) Any person not under the control of the employer to whom inor anic arsenic-contaminated clothing and e uipment is consigned for cleaning, f aun- dering, disposal or other purpose shal9 be informed in writing by the em loyer of the provisions of this Order and of the potentially harmful effects, incP uding carcinogenic effects, of exposure to inorganic arsenic. (C) The employer shall provide the rotective clothing required in Section 5214 (i) (1) , in a freshly laundered and Bry condition at least weekly, and daily if the employee works in areas where exposures are over 0.1 milli ams of inorganic arsenic per cubic meter of air or in areas where more fequent laundering is needed to revent skin irritation. (D) The em loyer sh a! 1 repair or replace the protective clothing and equip- ment as neede2 to maintain their effectiveness. removal from the change room. (G) Where inor anic arsenic com ounds with sigruficant vapor pressure such as arsenic tricfl loride are used, tK e employer shall develop a procedure i prescribing appropriate emergency action for the removal and disposition of arsenic trichloride-contaminated protective clothing andlor equipment. (H) The employer shall prohibit the removal of inorganic arsenic from pro- tective clothing or equipment by shaking or by the use of compressed air or other gases. (j) Housekeeping. Procedures shall be established and im lemented for the prompt and effective cleanup of inorganic arsenic spills an (! leaks and for the maintenance of all accessible working surfaces such as floors, bench tops, and hand rails as free as practicable of accumulations of inorganic arsenic. (1) Floors and other accessible surfaces contaminated with inorganic arsenic may not be cleaned by the use of compressed air, and shoveling and brushin ma be used only where vacuuming or other relevant methods have been trie 8 an B found not be effective. (2) The cleanin of’floors or other surfaces contaminated with inorganic arsenic particulate %y washing down with a hose is prohibited unless a fine spray has first been laid down. (3) Where cleaning is performed by vacuuming methods, a high efficiency internal filter (“HEPA”) or other appropriate means shall be uthzed for re- moval of inorganic arsenic from all air exhausted by the vacuum system or device. (4) Where a portable vacuum cleaning device is utilized, it shall be labeled in accordance with Section 5214(1) (3). i ...... I. .- .. TITLE8 GENERAL INDUmY SAFETY ORDERS 0 5214 (Rogirter 7% No. 1-4-79) (p. 442.6.73) .... (5) A written housekeeping and maintenance plan shall be kept which shall ...... list appropriate frequencies for carrying out housekee in operations, and for cleaning and maintaining dust collection equipment. Thp!e p an shall be available for inspection by authorized representatives of the Chief. (6 Periodic cleaning of dust collection and ventilation equi ment and check s of their effectiveness shall be carried out to maintain the er; ectiveness of the system and a notation kept of the last check of effectiveness and cleaning or maintenance. (7) Inorganic arsenic waste, scra , debris, bags, containers, or e uipment shall be disposed of in sealed and Pabeled bags or other closed an\ labeled containers which prevent dqersion of inorganic arsenic outside the container. Authority cited: Labor Code Section 142.3. Reference: Health and Safety Code 24230. (k) Hygiene Practices and Facilities. (1) Employees who work in a regulated area or who are otherwise subject to possible direct contact with inorganic arsenic shall be required to routinely exercise the following practices. (A) To wash their hands and face before eating. (B) To shower at the completion of the work shift and always before chang- ing into street clothes. (2) The stora e and consumption of food or beverages; the stora e, smoking, or chewing of to% acco products or other products for smoking or ca ewing; and the storage and application of cosmetics are prohibited in regulated areas. Drinkin fountains are permitted in regulated areas. (31 CLge rooms and shower facilities shall be provided for the use of empoyees working in a regulated area or who are otherwise required to shower or use personal protective clothing and equipment in accordance with this Order. (A) Change rooms shall conform with Section 3367. (B) Shower facilities shall conform with Section 3366 (h). (4) The employer shall provide for employees working in regulated areas, lunchroom -facilities which have a tem erature controlled, ositive pressure, filtered air supply, and which are rea dy accessible to empP oyees working in regulated areas. (5) The employer shall provide facilities for employees working in areas where exposure, without regard to the use of respirators, exceeds 0.1 milligrams of inorganic arsenic per cubic meter of air to vacuum their protective clothing and clean or change shoes wom in such areas before entering change rooms, lunchrooms or shower roorirs required by this subsection and shall assure that employees use such facilities. EXCEPI'ION: Workplaces where inorganic arsenic is reshicted to compounds with sig- nificant vapor pressure such as arsenic trichloride. (6) The employer shall assure that no employee is exposed to skin or eye contact with arsenic trichloride, or to skin or eye contact with liquid or particu- late inorganic arsenic which is likely to cause skin or eye irritation. Authority cited: Labor Code Section 142.3. Reference: Health and Safety Code 24230. -. .. . . I ;.. . $5214 GENERAL INDUSTRY SAFETY ORDERS TITLE8 (p. 442.6.74) (Rogirtor 78, No. 1242&m9) ( (I) Signs and Labels. (1) General. (A) Labels or signs required by other regulations or statutes may be used in addition to, or in combination with, signs or labels required by this subsection. (B) No statement shall a pear on or near any sign, label, or instruction required by this subsection wK ich contradicts or detracts from the effect of any required warning, information, or instruction. [f)%krances or approaches to a regulated area shall be posted with a sign bearing the following legend: DANGER (INSERT APPLICABLE CHEMICAL NAME) CANCERHAZARD AUTHORIZED PERSONNEL ONLY NO SMOKING OR EATING RESPIRATOR REQUIRED provisions of Section 6003 shall govern the design of by this paragraph. assure that si required by this aragraph are necessary so at the legend is rea b; y visible. (3) Labels. 8" (A) Precautionary labels shall be prominently affixed to containers of raw materials, intermediates, roducts, byproducts, mixtures, scrap, waste, debris, contaminated clothing an B any other material containing inorganic arsenic and the labels shall remain affixed whenever an such products or materials are sold, consigned, or distributed or otherwise reave a place of employment. EXCEITON: When the inorganic arsenic is encapsulated or bound within the product in such a manner as to make unlikely the possibility of exposure to airborne inorganic arsenic. Examples include semiconductors, light emitting diodes, and glass. (B) Labels required by this paragraph shall be legible and understandable and shall bear the following legend: DANGER CONTAINS INORGANIC ARSENIC CANCER HAZARD HARMFUL IF INHALED OR SWALLOWED USE ONLY WITH ADEQUATE VENTILATION OR RESPIRATORY PROTECTION (C) The label warning, CANCER HAZARD, required by Subsection 5214 (1) (3) (B) shall be at least one-half the height of the largest other lettering on the container or product and not less than &point type in any instance. Authority cited: Labor Code Section 142.3. Reference: Health and Safety Code 2A230. I TITLE8 GENERAL INDUSIXY SAFETY ORDERS $5214 ( (Rogirtw 81, No. -1) (p. 442.6.75) .'.. (m) Employee Information and Training. (1) Training Program. A training program shall be instituted for all em- ployees who may be exposed to inorganic arsenic above the action level without regard to respirator use or for whom there is the possibility of skin or eye irritation from inorganic arsenic. (A) The training pro am shall be provided within 60 days of the effective date of this Order or at tre time of an employee's initial assignment and at least annually thereafter. (B) The program shall include, as a minimum, the following information, instruction, and training in language which all affected employees can under- stand: 1. The information contained in A pen& A; 2. The quanti ,location, manner of use, storage, sources of exposure, and the specific nature o7 operations which could result in exposure to inorganic arsenic (. as well as my necessary protective steps; 3. Work and hygienic practices to be followed to preclude exposure to inor- ganic arsenic; 4. The purpose, pro r use, and limitations of respiratory protective equip- ment and protective cr othing and qui ment; 5. The purpose and a description oP the medical surveillance program as required by Section 5214(n); 6. The engineering controls and work practices associated with the em- pioyee's job assi ment; and 7. A review or this standard. i (2) Access to Training Materials. (A) A copy of this standard and its appendices shall be made readily available to all affected employees. (B) Any safety data sheets related to inorganic arsenic or'other hazardous substances utilized in processes covered by this standard available from a manu- facturer or supplier or developed by the employer shal1 be made available to all affected employees. (C) The employer shall provide, upon request, all materials relating to the employee information and training program to authorized representatives of i the Chief. (n) Medical Surveillance. (1) General. (A) The employer shall institute a medical surveillance program for the following employees: 1. All employees who are or will be exposed above the action level, without regard to the use of respirators, at least 30 days per year; and 2. All employees who have been exposed above the action level, without for 30 days or more per year for a total of 10 years or with the em loyer or predecessor employers of this stan ard. The determination of expo- sures prior to the effective date of this standardx shall be based upon prior exposure records, comparison with the first measurements taken after the ef- fective date of this standard, or comparison with records of ex osures in areas with similar processes, extent of engineering controls utilize s and materials used by that employer. i .*.- $5214 GENERAL INDUSIW SAFETY ORDERS TITLE 8 (p. 442.6.76) (Roghtor 81, No. 22-11 ( (B) The employer shall obtain the services of a California-licensed physician familiar with the occupational hazards of inorganic arsenic to vise all medical examinations and procedures required by rdomis subsection.Or super- (C) The employer shall provide all medical examinations and rdures without cost to the employee, without loss of pay and at a reasonab Pe time and place. (2) Initial Examinations. Within four months of the effective date of this standard, for employees initially covered by the medical provisions of this subsection, or thereafter at the time of initial assignment to an area where the employee is likely to be exposed over the action level at least 30 days per year, the employer shall provide each affected employee an opportunity for a medi- cal examination, including at least the following elements: (A) A work and comprehensive medical history, including smoking history; (B) A physical examination with special attention to skin, nose, respiratory . tract, lymph nodes, nervous system, and liver; (C) posterior-anterior chest X-ray (14-inch x 17-inch); i (D) Com lete blood count (CBC), urinalysis, and any other laboratory tests which the p K ysician determines are indicated; and (E) A sputum cytology examination. (3) Periodic Examinations. - (A) The employer shall provide each affected employee under 45 years of age with fewer than 10 years of exposure over the action level, without re ard to re irator use, an opportunity for an anriual medical examination, inclu %'ng the foTi owing elements: 1. Interim work and medical history, including smoking history; I 2. Interim physical examination; '.. 3. posterior-anterior chest X-ray (14inch x 17-inch); and 4. Complete blood count (CBC), urinalysis, and any other laboratory tests which the physician determines are indicated. (B) The employer shall provide each affected employee either 45 years of age or older or with 10 or more years of exposure over the action level, without regard to res irator use, with an opportunity for a semi-annual medical exami- nation, incluLg a sputum cytology examination in addition to the elements prescribed by Section 5214(n) (3) (A). (C) Whenever an affected employee has not taken the applicable medical examination prescribed by Section 5214(n (3) (A) or (n) (3) (B) within six (6) months preceding the termination of empI oyment, the employer shdi provide an opportunity for such examination upon termination of employment. (4) Additional Examinations. Whenever signs or symptoms of health prob- lems arise which the employee believes to be related to occupational exposure to inor anic arsenic, the employer shall provide the employee an opportunity for m e%'cal consultation from the physician. (5) Physician's Written Report. (A The employer shall obtain from the physician a written re ort interpret- ing 3,e results, insofar as they concern occupational hazards, oP each medical examination and roviding recommendations, if appropriate, of action to be taken by the empY oyer for the protection of the employee's health. I. I. -____-. _.. ------ TITLE 8 CEhrEHAI, INDUSTRY SAFETY ORDERS 0 5214 ( (Rqgirtrr 81. No. t2421J1) (p. 442.6.77) ...... ' (B) The employer shall instruct the physician not to reveal in the written .. opinion specific findings or diagnoses unrelated to occupational exposure. (C) The physician's written report shall include a statement that the em- ployee has been informed by the physician-of the results of the medical exami- nation and any medical conditions which require further explanation or treatment. (D) The empIoyer shall provide a copy of the physician's written'report to the affected emylo ee. (6) Information brovided to the Physician. The emplo er shall make the following information available to the physician prior to tK e conduct of any medical examination required by this subsection. (A) A copy of this standard and its ap ndices. (B) A description of the employee*s 8"uties as they relate to exposure to inorganic arsenic. i (C) For candidates for employment or new employees, a statement of the anticipated or estimated &hour, time-weighted average concentration of air- of the afkted em- nation. (0) Recordkeeping. (1) ?re Monitoring. The employer shall establish and maintain a record o all monitorin r uired by Section 5214(e). (A) This record shalfin3ude: 1. The dates, number, duration, location, and results of each of the samples taken, including a description of the sampling procedure used to determine re resentative employee exposure; A description of the sampling and analytical methods used and evidencc of Btheir accuracy; 3. The type of respiratory protective devices wom, if my; 4. Name, social security number, and job classification of employee(s) moni- tored and of all other employees whose exposure the measurement is intended to represent; and 5. The environmental variables that could affect the measurement of the employees exposure. 0 5214 GENERAL INDUSTRY SAFETY ORDEHS TITLE 0 (p. 442.6.713) (R.giat.r (1. No. 1242141) ( (B) The employer shall maintain these monitoring records for at least 40 years or for the duration of employment plus 20 years, whichever is longer. (2) Physician's Written Reports. (A) The employer shall establish and maintain an accurate record of the physician's written reports obtained in accordance with Section 5214(n) (5) for each affected emplo ee. The record shall include the name and social security number of the empr oyee and the fol!owinp;: 1. Results of any exposure monitorin done for that employee and the repre- sentative exposure levels supplied to ta e physician; and 2. Any employee medical complaints related to exposure to inorganic arsenic. (B) This record shall be maintained for at least 40 years or for the duration of employment plus 20 years, whichever is longer. (3) Medical Records. (A) The emplo er shall keep, or assure that the examining physician keeps, the following meB ical records: 1. A copy of the medical examination results including medical and work history required under Section 5214 (n); 2. A description of the laboratory procedures and a copy of any standards or guidelines used to interpret the test results or references to that information; 3. The initial X-ra ; 4. The X-ray for t ie most recent 9 years; and 5. Any X-rays with a demonstrated abnormality and all subsequent X-rays; 6. The initial cytologic examination slide and written descri tion; ( 7. The cytologic examination slide and written description Por the most re- cent 5 years; and 8. Any cytologic examination slides with demonstrated at pia, if such atypia persists for 3 years, and all subsequent slides and written Jescriptions. (B) The em loyer shall maintain or assure that the physician mointains those medical recor Bs for at Ieast 40 years or for the duration of employment plus 20 years, whichever is longer. (4) Availability. (A) The em loyer shall make available upon request all records re uired to be maintained gy this section to authorized representatives of the Chie? and the Director for examination and copying. (€3) Records required by this section shall be provided upon request to em- ployees, designated representatives, and authorized representatives of the Chief in accordance with Section 3204. TITLE8 GENERAL INDUSTRY SAFETY ORDERS 0 5214 ( (R.gi8t.r Dl, No. 124141) (p. 442.6.79) (5) Transfer of Recordkeeping. (A) Whenever an employer ceases to do business, all applicable records maintained under the requirements of this section shall be transferred to the for their continued maintenance. ceases to do business and there is no successor employer, transmitted to the Director. (C) At the e iration of the retention period for the records required to be maintained by% section, the employer shall notify the Director at least 3 months prior to the disposal of such records and shall transrnit those records to the Director if he requests them within that period. (D) The employer shall also comply with any additional requirements in- volving the transfer of records set forth in Section 3204. (p Observation of Monitoring. During any observation of monitoring by an Bected employee or em loyees, or their representative, pursuant to Title (:, 8, Section 340.1, California A LtrativeCode, the employer shall provide the observer with personal protective clothing or equipment required to be worn working in the area, assure the use of such clothin and equip- uire the observer to comply with all other applicabP e safety and Authority cited: Labor Code Section 142.3. Reference: Health and Safety Code 24230. (q A pendices. The information contained in the ap ndices to this stan daar is not intended, by itself, to create any additionape obligations not otherwise imposed by the standard or to detract from any such obligation. ( (r) Startu Dates. 1. Gener8 The startu dates of requirements of this standard shall be the effective date of this stan ard unIess another startup date is either prescribed elsewhere in this standardB or in this subsection. 2. Monitoring. Initial monitoring (cf, Section 5214(e)(2)) shall be com- pleted within 30 days of the effective date of this standard. 3. Regulated Areas. Regulated areas (cf, Section 5214(f)) required to be established as a result of initial monitoring shall be set u as soon as possible after the results of that monitoring is known but no later tRan 60 days from the effective date of this standard. 4. Compliance Program. The written program required b Section 5214( ) (2) (A) of this standard as a result of initial monitoring sh aibe made availafl le for inspection and copying as soon as possible but no later than 60 days from the effective date of this standard. 5. Hy 'ene and Lunchroom Facilities. Construction plans for change rooms, sa owers, and lunchroom facilities shall be completed within 120 days of the effective date of this standard and these facilities shall be constructed and in use no later than July 1,1979. However, if as part of the compliance plan it is predicted by an independent engineering firm that engineering controls and work practices will reduce exposures to or below the permissible exposure limit by December 31,1979 for affected employees, then such facilities need not be completed until one ear after the engineering controls are completed or December 31,1980, w h'chever is earlier, if such controls have not in fact suc- ceeded in reducing exposure to or below the permissible exposure limit. I .. .. -- -- 0 5214 GENERAL INDUSTRY SAFETY ORDERS (p. 442.6.80) (Register 81, No. t242141) APPENDIX A INORGANIC ARSENIC SUBSTANCE INFORMATION SHEET I. SUBSTANCE IDENTIFICATION A. Substance. Inorganic Arsenic B. Dcfini tion. Copper acetoarsenite, arsenic and all inorganic compounds containing arsenic except arsine, measured as arsenic (As). C. Permissible Exposure Limit. 10 micrograms per cubic meter of air as determined as an average over an 8-hour eriod. No employee may be ex osed to any skin or eye contact with arsenic tricEl oride or to skin or eye contact Pikely to cause skin or eye irritation. D. Regulated Areas. Only employees authorized by your employer should enter a regulated area. 11. HEALTH HAZARD DATA ( A. Comments. The health hazard of inorganic arsenic is high. B. Ways In Which Inorganic Arsenic Affects Your Body. Exposure to air- borne inorganic arsenic may cause lun cancer, and it can be a skin irritant. Inorganic arsenic may also affect your %ody if swallowed. One compound in particular, arsenic trichloride, is especially dangerous because it is highly corro- sive and it can be absorbed readily throu h the skin. Because inorganic arsenic is a poison, you should wash your hands ta oroughly prior to eating or smoking. 111. PROTECTIVE CLOTHING AND EQUIPMENT A. Respirators. Respirators will be provided by your employer at no cost to ( you for routine use if your employer is in the process of implementing engineer- ing and work practice controls 3r where engineering and work practice con- trols are not feasible or insufficient. You must wear respirators for non-routine activities or in emergency situations where you are likely to be exposed to levels of inorganic arsenic in excess of the permissible exposure limit. Since how well your respirator fits your face is very important, your em loyer is required to conduct fit tests to make sure the respirator seals pro er y when you wear it. These tests are simple and rapid and will be explaine to you during training sessions. xf B. Protective clothing. If you work in a regulated area, your employer is required to rovide at no cost to you, and you must wear, appropriate, clean, protective cP othing and equipment. The purpose of this equipment is to pre- vent ou from bringing to our home arsenic-contaminated dust and to protect your L ody from repeated sE in contact with inorganic arsenic likely to cause skin irritation. This clothing should include such items as coveralls or similar full- body clothing, loves, shoes or coverlets, and aprons Protective equipment should include f:ace shields or vented goggles where eye injury may occur. 11'. HYGIENE FACILITIES AKD PRACTICES You must not eat, drink, smoke, chew gum or tobacco, or apply cosmetics in the regulated area, except that drinking water is permitted. If you work in a regulated area your employer is required to provide lunch rooms and other areds for these purposes. If !sou \i?orkin a regulated area, your employer is required to provide showers, \\*aohingfacilities, and change rooms. You must wash your face and hands before ciitirig and must showyer at the end of the \cork shift. Do not take used protective cblothinv nllt nf rh2nop rnnmc tiGthniit t-rjiir Pmnln\mr'c normiccinn Vntrr om- GENERAL INDUSTRY SAFETY ORDERS 0 5214 ( E, No. 1242141) (p. 442.6.81) V. SIGNS AND LABELS Your employer is required to post warning signs and labels for your protec- tion. Signs must be osted in regulated areas. The signs must warn that a cancer hazard is present, t Kat on1 authorized employees may enter the area, and that no smoking or eating is dowed, and that respirators must be worn. VI. MEDICAL EXAMINATIONS If your exposure to arsenic is over the action level at least 30 days er year, or your have been exposed to arsenic for more than 10 years over t Ke action level, your employer is required to provide you with a medical examination. The exmination shall be every 6 months for em loyees over 45 ears old or with more than 10 years exposure over the action Yeve1 and annua5 y for other covered emplo ees. The medical examination must include a medical history; a chest x-ray; sl in examination; nasal examination and sputum cytology exam (,' for the earl detection of lung cancer. The cytolo exams are only included in the initi sexamination and examinations given Bter you are either 45 years or older or have 10 or more ears employment over the action level. The examining physician will provi Be a written opinion to your employer inter ret- ing the results of the medical exams. You should also receive a copy oP this opinion. The physician must not tell your employer any conditions he detects unrelated to occupational exposure to arsenic but must tell you those condi- tions. VII. OBSERVATION OF MONITORING i Your employer is required to monitor your exposure to arsenic and you or your re resentatives are entitled to observe the monitoring procedure. You are entitleB to receive an explanation of the measurement procedure, and to record the results obtained. When the monitoring procedure is taking place in an area where respirators or personal protective clothing and equipment are required to be worn, you must also be provided with and must wear the protective clothing and equipment. VIII. ACCESS TO RECORDS You or your representative are entitled to records of your exposure to inor- ganic arsenic u on request to your employer. Your medical examination records can be Purnished to you, your physician, or any other individual or organization that you designate if you request your employer to provide them. IX. TRAINING AND NOTIFICATION Additional information on all of.these items plus training as to hazards or exposure to inorganic arsenic and the engineering and work ractice controls associated with your job will also be provided by your empP oyer. If you are exposed over the permissible exposure limit, your employer must inform you of that fact and the actions he is taking to reduce your exposures. i $5214 GENERAL INDUSTRY SAFETY ORDERS (p. 442.6.82) (Rwirtrr 81. No.TITLE8 124161) APPENDIX B SUBSTANCE TECHNICAL GUIDELINES ARSENIC, ARSENIC TRIOXIDEJ ARSENIC TRICHLORIDE (THREE EXAMPLES) I. Physical and Chemical Properties A. Arsenic (metal). 1. Formula: As. 2. A earance: Gray metal. 3. JP e ting point: Sublimes without melting at 613%. 4. Specific Gravity: (HSO = 1):5.73. 5. Solubility in water: Insoluble. B. Arsenic Trioxide. 1. Formula: AszO3. (AsrOs). 2. Ap earance: White powder. 3. MeP ting point: 315'C. 4. Specific Gravity (H20= 1):3.74. 5. Solubility in water: 3.7 grams in l0cc of water at 20°C. - C. Arsenic Trichloride (liquid). 1. Formula: AsC13. 2. A earance: Colorless or pale yellow liquid. . 3. 9Pe ting point -8.5"C. 4. Boiling point: 130.2"C. 5. Specific Gravity (HzO = 1): 2.16 at 20°C. 6. Vapor pressure: 10" Hg at 23.5%. 7. Solubili in Water: Decomposes in water. 11. Fire, Ekp7 osion and Reactivity Data. A. Fire: Arsenic, Arsenic Trioxide and Arsenic Trichloride are nonflammable. B. Reactivity: 1. Conditions Contributing to Instability: Heat. 2. Incompatibility: Hydrogen gas can react with inorganic arsenic to form the highly toxic gas arsine. I 111. Monitoring and Measurement Procedures. Samples collected should be full shift (at least 7-hour) samples. Sampling should be done using a rsonal sampling pump at a flow rate of 2 liters per minute. Samples shouldK collected on 08 micrometer pore size membrane filter (37mm diameter). Volatile arsenicals such as arsenic trichloride canbe most easily collected in a midget bubbler filled with 15 ml. of 0.1 Nsodium hydroxide. The method of sampling and analysis should have an accuracy of not less than +25 percent (with a confidence limit of 95 percent) for 10 micro ams cubic meter of air (10 pg/M3) and +35 percent (with a confidence &rrmt or:; percent) for concentrations of inorganic arsenic between 5 and 10 pg/M3. I -- '. a . .- TITLE 8 GENERAL INDUSIXY SAFETY ORDERS 0 5214 (Regirtor 79. No. 124479) (p. 442.6.83) APPENDIX C MEDICAL SURVEILLANCE GUIDELINES I. General Medical examinations are to be provided for all employees exposed to levels of inorganic arsenic above the action level (5 pg/M3) for at least 30 days per year (which would include, among others, all em loyees who work in regulated areas). Examinations are also to be provided to 2 employees who have had 10 years or more exposure above the action level for more than 30 days per year while working for the present or redecessor employer though they may no longer be exposed above the lever An initial medical examination is to be provided to all such employees within 4 months of the effective date of the standard. In addition, an initial medical (.. examination is to be provided to all employees who are first assigned to areas in which worker exposure will probably exceed 5 pg/M3 (after the effective date of this standard) at the time of initial assignment. In addition to its immediate-diagnostic usefulness, the initial examination will provide a baseline for comparing future test results. The initial examination must include as a minimum the followin elements: (1) A work and m eti'cal history, including a smoking history; (2) A physical examination with special attention to skin, nose, respiratory tract, lymph nodes, nervous system, and liver; (3) Posterior-anterior chest x-ray (14-inch x 17-inch); (4) Complete blood count (CBC), urinalysis, and any other laboratory tests which the physician determines are indicated; and (5) A sputum cytology examination. Periodic examinations are also to be provided to the employees listed above. The periodic examinations shall be given annually for those covered empIoyees 45 years of age or less with fewer than 10 years employment in areas where employee exposure exceeds the action level (5 examinations need not include sputum cytology and only medical history is required. Periodic examinations for other covered em loyees, shall be provided every six (6)months. These examinations shall inchB e all tests required in the initial examination, except that the medical history need only be updated. The examination contents are minimum requirements. Additional tests such as lateral and oblique X-rays or pulmonary function tests may be useful. For workers exposed to three arsenicals which are associated with lymphatic cancer, copper acetoarsenite, potassium arsenite, or sodium arsenite the examination should also include palpation of superficial lymph nodes and complete blood count. 11. NONCARCINOGENIC EFFECE . The standard is based on minimizing risk of e sed workers dying of lung cancer from exposure to inorganic arsenic. It wixeo also minimize skin cancer from such exposure. The following three sections uoted from "Occupational Diseases: A Guide to Their Recognition", Revise1 Edition, June 1977, National Institute for Occupational Safety and Health is included to provide information on the nonneo lastic effects of exposure to inorganic arsenic. Such effects should not occur i fpthe OSHA standards are followed. $5214 GENERAL INDUSI’RY SAFETY ORDERS TITLE8 (p. 442.6.84) (Rogirtu 78, No. 12-78) c A. Local-Trivalent arsenic compounds are corrosive to the skin. Brief con- tact has no effect but prolonged contact re-dts in a local hyperemia and later vesicular or pustular eru tion. The moist mucods membranes are most sensitive to the irritant action. eonjunctiva, moist and macerated areas of skin, the eyelids, the angles of the ears, nose, mouth, and respiratory mucosa are also vulnerable to the irritant effects. The wrists are common sites of dermatitis, as are the genitalia if personal hygiene is r. Perforations of the nasal septum may occur. Arsenic trioxide and pentoxi R“e are capable of roducing skin sensiti- ____. - ... .- zation and contact dermatitis. Arsenic is also capable oP producing keratoses, expecially of the alms and soles. B. Systemic-&e acute toxic effects of arsenic are generally seen followin ingestion of inorganic arsenical compounds. This rarely occurs in an indusd setting. Symptoms develop within ‘/n to 4 hours following in estion and are usually characterized by construction of the throat followe tf by dysphagia, (- epi astric pain, vomiting, and watery diarrhea. Blood may appear in vomitus I! anI! stools. If the amount ingested is sufficiently high, shock may develop due to severe fluid loss, and death may ensure in 24 hours. If the acute effects are survived, exfoliative dermatitis and peripheral neuritis may develop. Cases of acute arsenical poisoning due to inhalation are exceedin ly rare in industry. When it does occur, respiratory tract sympto“gh, ca est pain, dyspnea giddiness, headache, and extreme general weakness precede gastroin- testinal symptoms. The acute toxic symptom of trivalent arsenical poisoning are due to severe inflammation of the mucous membranes and greatly in- creased permeability of the blood capillaries. i Chronic arsenical poisoning due to ingestion is rare and generally confined to patients taking prescribed medications. However, it can be a concomitant of inhaled inorganic arsenic, from swallowed sputum, and improper eating habits. Symptoms are weight loss, nausea and diarrhea alternating with constipation, pigmentation and eruption of the skin, loss of hair, and peripheral neuritis. Chronic hepatitis and cirrhosis have been described. Polyneuritis may be the salient feature, but more frequently there are numbness and parasthenia of “glove and stocking” distribution. The skin lesions are usually melanotic and keratotic and may occasionally take the form of an intradermal cancer of the squamous cell , but without infiltrative properties. Horizontal white lines (striations) on tx” e fingernails and toenails are commonly seen in chronic arseni- cal poisoning and are considered to be a diagnostic accompaniment of arsenical polyneuritis. Inhalation of inorganic arsenic compounds.is the most common cause of chronic poisoning in the industrial situation. This condition is divided into three phases based on signs and symptoms. First Phase: The worker com lains of weakness, loss of appetite, some nausea, occasional vomiting, a sense oP heaviness in the stomach, and some diarrhea. Second Phase: The worker complains of conjunctivitis, a catarrhal state of the mucous membranes of the nose, larpx, and respiratory passage. Coryza, hoarseness, and mild tracheobronchitis may occur. Perforation of the nasal septum is common, and is probably the most ical lesion of the upper respira- tor tract in occupational exposure to arsenic9 dust. Skin lesions, eczematoid an dr allergic in type, are common. $5215 GENERAL INDUmY SAFEIY ORDERS TITLE8 (p. 442.6.86) (R.gi8tor 0. No. tolswjlfc necessary diagnostic investigation should be readdy available 8s well as chest ph sicians, surgeoils, radiologists, pathologists and immunotherapists to pro- vid e any necessary treatment services. NOTE: Authority cited: Section 142.3,Labor Code. Reference: Section 142.3, Labor Code. HISTORY: 1. Renumbering of Section 5214 to Section 5185 filed 5-3-78 as procedural and organiza- tional; effective upon filing (Register 78, No. 18). For history of former Section 5214, see Register n,No. 41. 2. New section filed 3-19-79; effective thirtieth day thereafter (Register 79, No. 12). 3. Amendment of subsection (a)(3) filed 9-1580; effective thirtieth day thereafter (Register 80, No. 38). 4. Amendment of subsection (0) and Appenh A (VIII) filed 3-20-81; effective thirti- eth day thereafter (Register 81, No. 12). 5. Amendment of subsections (a)(6), (a)(7), (b), (d)(l)(C), (e)(2), (h) and (n) (5) (A) filed 5-2981; effective thirtieth day herder (Register 81, No. 22). 6. Editorial correction of subsection (b) filed 3-3-83 (Register 83, No. 10). 5215. 4,4’-Methylenebis (2-chloroaniline). a) Scope and Application. I 1) This section establishes requirements for the control of employee expo- sure to 4,4’-methylenebis (%chloroaniline),MBOCA, Chemical Abstracts Serv- ice Registry No. 101144. (2 This section a plies to the manufacture, packaging, repackaging, storage, han g and use oP MBOCA, but does not apply to: (A)L Fabricated products; or (B) The storage or transportation of MBOCA in sealed, unbroken containers except for labeling of containers under Section 5215(1) (4), reporting of use c under Section 5215(n) (1) and preparation of emergency plan under Section 5215 (h) (4). (3) The r uirements of this section are subject to the provisions of the Occupational7 arcinogens Control Act of 1976 (Health and Safety Code, Divi- sion 20, Chapter 2). b) Definitions. uthorized Person. Any person specifically authorized by the employer to handleL or use MBOCA or to enter a controlled access area or any erson entering such an area as a designated re resentative of employees Por the i purpose of exercising an opportunity to o\ serve monitoring and measuring procedures. Chief. The Chief of the Division of Occupational Safety and Health, P.O. Box 603,San Francisco, CA 94101. Controlled Access Area. An area where entry and exit are restricted and controlled for the p ose of limitin occupational exposure to MBOCA. Engineering Contro”p s. Methods of controlling occupational exposure to in- ‘urious materials or conditions by means of general or local exhaust ventilation, Ly process modification, or by isolation or enclosure of health hazard-producing o ration or machinery. Engineering controls do not include employee person- grotection. Work Practice Controls. Methods of controlling occupational exposure to injurious materials or conditions by means of written procedures specifjing handling, employee personal protection and personal hygiene. State of California CALIFORNIA ADMINISTRATIVE CODE TITLE 22. SOCIAL SECURITY Chapter 4. Environmental Health 2777E ( b) R uests for waiver shall be made in wri and shall include: of the processing method 3 of the waste before and after treatment. waste before and after treatment. com sitions of any hazardous residues which are or wgP 'ch are generated as result of treatment of the i waste. .. method to be used for disposal of the treated waste and of any Department may obtain and analyze samples of the waste collected after treatment. (d) The Department shall continue, grant or deny each request within 30 days (ej The Department may waive the fee for ctspo~alof a waste for a period up to 12 months, rovided the treatment and dqosal method and the chemical ( composition of tge waste do not change during that period. Article 9. Hazardous Wastes and Hazardous Materials 66680. Lists of Chemical Names and Common Names. (a) A waste that meets the definition of hazardous waste presented in Sec- tion 25117 of the Health and Safe Code or satisfies any of the criteria of hazardous waste presented in Artic1 e 11 of this chapter shall be considered a hazardous waste whether or not the waste is cited in this article. Such a waste shall be handled and disposed of according to the provisions of this chapter. (b) A waste that meets the definition of extremely hazardous waste present- I ed in Section 25115 of the Health and Safety Code or satisfies an of the criteria of extremely hazardous waste resented in Article 11 of this cLa pter shall be considered an extremely hazarfI ous waste whether or not the waste is cited in this article. Such a waste shall be handled and dqmsed of accordmg to the provisions of this cha ter. (c) The potential Ldous property of a material cited in the List of Chemical Names or the List of Common Names is indicated in the list as foUows: (T) toxic, (C) corrosive, (F) ignitable and (R) reactive. An asterisk (*) in Section =(d) denotes an extremely hazardous waste. All letters in trade- mark names are capitalized. ! (d) List of Chemical Names: i. Acetaldehvde (TJ) 2. Acetic acid (T,C$) 3. Acetone, Propanone (F) 4. I 5. 6. I 7. a. 9. 10. 11. *Acrolein, Aqualin (TJ?) 0- ENVIRONMENTAL HEALTH TITLE22 (p. 1soo.56) (Roglrtor 1,No. 2-1-tub) f 12. *Acrylonitrile (T,F) L 13. *Adiponitrile (T) 14. *Aldrin; 1,2,3,4,10 10-Hexachloro-l,4,4a,!5,8,8a-hexahydro- 1,4,5,8-endo-exðanona hthdene (T) 15. *Alkyl aluminum chloride (C,p;. ,R) 16. 'Alkyl aluminum compounds (C,F,R) 17. Allyl alcohol, 2-Propen-1-01 (T,F) 18. Allyl bromide, 3-Bromopropene (T,F) 19. Allyl chloride, 3-Chlorory!ne (T,F) 20. Allyl chlorocarbonate, chloroformate (T,F) 21. *Allyl trichlorosilane (T,C,i ,R) 22. Aluminum ( wder) (F 23A. Aluminumcti oride (T,L ) 23B. *Aluminum chloride (anhydrous) (T,C,R) 24. Aluminum fluoride (T,C) 25. Aluminum nitrate (T,F) 26. *Aluminum ho hide, PHOSTOXIN (T,F,R) 27. *CAminodipKT eny , CADP (T) 28. *%Aminopyridine (T) 29. *Ammonium arsenate (T) 30. *Ammonium bifluoride (T,C) 31. Ammonium chromate (T,F) 32. Ammonium dichromate, Ammonium bichromate (T,C,F) 33. Ammonium fluoride (T,C) 34. Ammonium hydroxide (T,C) 35. Ammoniummolybdate (T) 36. Ammonium nitrate (F,R) 37. Ammonium perchlorate (F,R) 38. Ammonium permanganate (T,F,R) 39. Ammonium persulfate (F,R) * 40. Ammonium picrate (T,R) 41. Ammonium sulfide (T,C,F,R) 42. n-Amyl acetate, 1-Acetoxypentane (and isomers) (T,F) 43. n-Amylamine, 1-Aminopentane (and isomers) (T,F) 44. n-Amyl chloride, 1-Chloropentane (and isomers) (T,F) 45. n-Amylene, 1-Pentene (and isomers) (T,F) 46. n-Amyl mercaptan, I-Pentanethiol and isomers) (T,F) 47. n-Amyl nitrite, n-Pentyl nitrite (an6 isomers) (T,F) 48. *Am 1 trichlorosilane (and isomers) (T,C,R) 49. de,Aminobenzene (T) 50. Anisoyl chloride (T,C) 51. Anthracene (T) 52. Antimony (T) 53. Antimonycompounds (T) 54. *Antimony pentachloride IT,C,R) 55. *Antimony pentduoride (T,C,R) 56. Antimony pentasulfide (T,F) 57. Antimony potassium tartrate (T) 58. Antimony sulfate, Antimony trisulfate (T,F) I .' ' .: .. ...... I, . .. 59. Antimony trichloride, Antimony chloride (T,C) .. 60. Antimony hifluoride, Antimony fluoride (T,C) .. 61. Antimony trioxide, Antimony oxide (T) 62. Antimony trisulfide, Antimony sulfide (T,F,R) .. 63. *Arsenic (T) 64. *Arsenic acid and salts (T) *. 65. *Arsenic compounds (T) 66. 'Arsenic pentaselenide (T) 61. *Arsenic pentoxide, Arsenic oxide (T) 68. *Arsenic sulfide, Arsenic disulfide (T) 69. *Arsenic tribromide, Arsenic bromide (T) 70. *Arsenic trichloride, Arsenic chloride (T) 71. *Arsenic triiodide, Arsenic iodide (T) -~ . 72. *Arsenic trioxide, Arsenious oxide (T) 73. *Arsenious acid and salts (T) 74. *Arsines (T) 75. Asbestos (includin chrysotile, amosite, crocidolite, tremolite, anthop hyllite, and actin0E le) (T) 76. *MODFUN, 3-Hydroxy-N-ciscrotonamide(T) 77. Barium (T,F) 78. Bariumazide T,R) 79. Barium bromi6 e (T) 80. Barium carbonate (T) - 81. Barium chlorate (T,C,FJI) 82. Barium chloride (T) t 83. Barium chromate (T) 84. Bariumcitrate (T 85. Barium compounds (soluble) (T) 86. *Barium c anide (T) 87. Barium Huoride (T) 88. Barium fluosilicate (T) 89. Barium hydroxide (T) 90. Barium iodide (T) 91. Barium manganate (T) 92. Barium nitrate (T,F) 93. Barium oxide, Barium monoxide (T) 94. Barium perchlorate (T,F,R) 95. Barium permanganate (T,F,R) 96. Bariumperoxide (T,F,R) 97. Barium phosphate (T) 98. Barium stearate (T) 99. Barium sulfide (T) 100. Barium sulfite (T) 101. Benzene (T.F) 102. *Benzene hexachloride, BHC; 1,!2,3,4,5,&Hexachloroyclohexane (T) 103. *Benzenephosphorousdichloride (T,R) 104. Benzenesulfonic acid (T) 105. *Bemidhe and salts (T) 106: *Benzotrifluoride, Trifluoromethylbenzene (T,F) 101. *I 3enzoyl chloride (T,C,R) 108. 13 enzo 1 peroxide, Dibenzoyl peroxide (T,F',R) 109. 1a mzy r bromide, alpha-Bromotoluene (T,C) 110. Ia lenzyl chloride, alpha-Cblorotoluene (T) 111. *I 3 1 chlorocarbonate, Benzyl chloroformate (T,C,R) 112. *I 3eery 'um (TJ) 113. *I3 erylliumchloride T) 114. *I3 erylliumcompoun $s (T) 115. *I 3eryllium copper (T) 116. *I 3eryllium fluoride (T) 117. *I 3eryliium hydride (T,C,F',R) 118. *I 3eryllium hydroxide (T).. 119. *Be$lium osde (T) ' 120. *BID" Dicrotophos, 3- (Dimethylamino)-1-methylhxo-1-propenyl dimeth \phosphate (T) 121. *bis (Cdoromethyl) ether, Dichoromethylether, BCME (T) CEREWET, Ceresan liquid (T) dimethyl phosphate (T) 1%. *Boranes (T,F,R) 121. *Bordeaux arsenites (T) 128. *Boron trichloride, Trichloroborane (TI-) 129. *Boron trifluoride (T,C,R) 130. Bromic acid (T) 131. *Bromine (T,C,F) 132. *Bromine pentafluoride (T,C,F,R) 133. *Bromine trifluoride (T,C,F,R) 134. *Brucine, Dimethoxystrychnine (T) 135. 1,!&4Butanetriolhinitrate (R) 136. n-Butyl acetate, 1-Aceto butane (and isomers) (T) 137. n-Butyl alcohol, 1-Butano7 (and isomers) (T) 138. n-Butyl amine, 1-Aminobutane (and isomers) (T) 139. n-Butyl formate (and isomers (T) 140. tert-Butyl hydroperoxide (and isomers) (T,F) 141. *n-Butyllithium (and isomers) (T,C,F,R) 142. n-Butyl mercaptan, 1-Butanethiol and isomers) (T,F) 143. tert-Butyl peroxyacetate, tert-Buty racetate (F,R) 144. tert-Butyl peroxybenzoate, tert-ButyI, perbenzoate (F,R) 185. tert-Butyl ryalate(F,R) 146. *n-Butyltric or0 * ane (C,F,R) 147. para-tert-Butyl toluene (T) 148. n-Bu aldehyde, n-Butanal (and isomers) (T,F) 149. *Cacor ylic acid, Dimethylarsinic acid (T) 150. *Cad" ( wder) (T,F) 151. Cadmium cE oride (T) 152. *Cadmium compounds (T) 153. *Cadmium c anide (T) 154. Cadmium Huoride (T) I TITLE22 ENMRONMENTAL~TH 1R-W Nn &l-1246) 155. Cadmiumnitrate (TJ?,R) 156. Cadmium oxide (T) 157. Cadmium phosphate (T) 158. Cadmium sulfate (T) 159. *Calcium (F,R) \ 160. *Calcium arsenate, PENSAL (T) 161. *Calcium arsenite (T 162. *Calcium carbide (C,'F ,R) 163. Calcium chlorate (F,R) 164. Calcium chlorite (F) 16. Calciumfluoride (T) 166. *Calcium hydride (C,F,R) 161. Calcium hydroxide, Hydrated lime 168. *Calcium hypochlorite, Calcium (dry) (T,C,F,R) 160. Calcium molybdate (T) ( 170. Calcium nitrate, Lime nitrate, Nitrocalcite (F,R) 171. Calcium oxide, Lime (C) 172. Calciumpermanganate (TJ? 173. Calcium peroxide, Calcium 'oxide (C,F) 174. *Calcium phosphide (T,F,R) 175. Calcium resinate (F) 176. Caprylyl peroxide, Octyl roxide (F) 177. *Carbanolate, BANOL,2 (5 ord,!jdirnethylphenyl methylcarbamate 178. Ebon disulfide, Carbon bisulfide (T,F) 179. Carbon tetrachloride, Tetrachloromethane (T) 180. *Carbo henothion, TRITHION, S[[ (4Chlorophenyl) thiobethyl] 0, Ode51 yl phosphorodithioate (T 181. Chloral hydrate, Trichloroacetald ehyde (h drated) (T) 182. *Chlordan; 1,2,4,5,6,'7,8,8-Octachloro4,7-me~o-3a,4,7,7a-tetrahydr~ indane (T) 183. *Chlorfenvinphos, Compound 4072,2Chloro-l-(2,edichlorophenyl) vi- n 1 diethyl hosphate (T) 184. *ciiorine @,R) 185. *Chlorine 'oxide (T,C,F,R) 186. *Chlorine pentafluoride (T,C,F,R) 187. *Chlorine trifluoride (T,C,F,R) 188. *Chloroacetaldehyde (T,C) 189. *al ha-Chloroacetophenone, Phenyl chloromethyl ketone ('I) 190. *Cf; oroacetyl chloride (T,C$) 191. Chlorobenzene (T,F) 192. para-Chlorobenzoyl 193. *ortho-ChlorobenzyliBeroxide ene malonitrile, OCMB (T) 194. Chloroform, Trichloromethane T) 195. *Chloropicrin, Chlorpicrin, Tricd oronitromethane (T) 196. *Chlorosulfonic acid (T,C,F,R) I 197. Chloro-ortho-toluidine, 2-Amin&hlorotoluene (T) 198. Chromic acid, Chromium trioxide, Chromic anhydride (T,C,F) 199. Chromic chloride, Chromium trichloride (T) 4- ENVIR0"TALHEALTH TITLE22 (p. 1800.60) (Rwim86, No. b-l-luI) HlO. Chromic fluoride, Chromium trifluwide (T) < 201. Chromic hydroxide, Chromium hydroxide (T) 2M. Chromic oxide, Chromium oxide (T) e(x3. Chromic sulfate, Chromium sulfate (T) 204. Chromium com unds (T,C,F) 205. +Chromyl chlori re, Chlorochromic anhydride (T,C,F,R) 206. Cobalt (powder) (T,F) 207. Cobalt compounds (T) 208. Cobaltous bromide, Cobalt bromide (T) 209. Cobaltous chloride, Cobalt chloride (T) 210. Cobaltous nitrate, Cobalt nitrate (T,F 211. Cobaltous resinate, Cobalt resinate (r' ,F) 218. Cobaltous sulfate, Cobalt sulfate (T) 213. Cocculus, Fishberry, Picrotoxin (T) 215. *Copper acetoarsenite, Paris green (T) 216. Copper acetylide T,R) 217. +Copper arsenate, bpric arsenate (T) 218. *Copper arsenite, Cupric arsenite (T) 219. Copper chloride, Cupric chloride (T) 220. Copper chlorotetrazole (T,R) 221. Copper compounds (T) 222. *Copper cyanide, Cupric cyanide (T) 223. Copper nitrate, Cupric nitrate (T,F,R) 224. Copper sulfate, Cupric sulfate, Blue vitriol (T) 225. +Coroxon; ortho,ortho-Diethyl-ortho-(3-chloro4methylcoumarin-7-y1) hosphate (T) 226. +%umafuryl, FUMARIN, 3-[1- (2Furanyl)3-oxobutyl]l4-hydroxy-2H- 1-benzopyran-%ne (T) 221. *Coumatetralyl, BAYER 25634, RACUMIN SI, 4Hydroxy3-(1,2,3,4tet- rahydro-1-na hthalenyl)-2H-l-benzopyran-20ne (T) 228. *Crimidine, C~STRIX,~~oro+iimethylamino+methylpyrimidine lT) 229. *&tonaldehyde, kButenal (T) 230. Cumene, Is0 ropy1 benzene (T,F) 231. Cumene hy operoxide; alpupha-Dimethylbenzyl hydropero~de 6: i 232. p.pnethylene diamine (T) 233. *Cyanide salts (T 234. cyanoacetic acidiMalonic nitrile (T) 235. +Cyanogen (T,F,R 236. Cyanogen bromi e, Bromine cyanide (T) 237. Cyanuric triazide (T,R) 238. Cycloheptane (T,F) 239. Cyclohexane (T,F) 240. Cyclohexanone peroxide (F) 241. *Cyclohexenyltrichlorodme (T,C,R) 242. *Cycloheximide, ACTlDIONE (T) IA3. 'Cyclohexyltrichlorosilane (T,C,R) 244. Cyclopentane (T,F) TITLE22 ENVIRONMENTAL HEALTH 0- 4R-kt.r 1. NO. kl-lm) (p. 1800.61) I W. Cyclopentanol (F 246. Gglopentene k ) 247. D T; l,l,l-Tric oro-2&bis(chlorophen 1 ethane (T 248. *DDVP, Dichlorvos, VAPONA, Dimethyrl 'chloroviny 1 phosphate (T) 249. *DecabOrane (T,F,R) 250. DECALIN, Decahydronaphthalene (T) I\ 251. *Demeton, SYSTOX (T 252. *Demeton-S-methyl one, METAISOSYSTOX-SULFON, S-[% (ethyl- sulfonyl) ethyl] 0,O-dimethyld hosphorothioate (T) 253. Diazodinitro henol, DDNP, 2fs iazo-4,6dinitrobenzene-l-oxide (T,R) 254. *Diborane, DiL ron hexahydride (T,R) 255. *1,2-Dibromo3chloropropane, DBCP, FUMAZONE, NEMAGON (T) 256. n-Dibutyl ether, Butyl ether (and isomers) (T,F) 251. Dichlorobenzene (ortho, meta, para) (T) 258. *3,3-Dichlorobenzide and salts, DCB (T) 259. l&Dichloroethylene; l&Dichloroethene (TJ?) ( a.Dichloroethyl ether, Dichloroether (T,F) 261. Dichloroisoc anuric acid, Dichloro-S-triazine-2,4,Wione (T,F) 262. Dichlorome ane, Methylene chloride (T) 263. *2,4DichlorophenoxyaceticK acid; 2,4D (T 264. l&Dichloropropane, Propylene dichlorid e (TJ?) 26!i 1,3-Dichloropropylene; 1,3-Dichloropropene (T,F) 266. Dicumyl peroxide (F,T) 267. *Dieldrin; 1,2,3,4,lO,lO-Hexachlor0-6,7epoxy-1,4,4a,5,6,7,8,8aa~y&o- 1,kndo, ex&,8dimethanonaphthalene (T ( 268. *Diethylaluminum chloride, Aluminum dietk yl monochloride, DEAC 'F,!J 'F,!J 268. Die ylamine (T,F 270. 'Diethyl chloroviny1 phosphate, Compound 1836 (T) 271. *Diethyldichlorosilane (T,CJ?,R) 272. Diethylene glycol dinitrate (T,R) ether (T) 278. fluoride (T) 281. Dimethylamine, DMA (TJ?) 282. Wimethylaminoazobenzene, Meth 1 yellow (T) 283. *Dimethyldichlorosilae,~ichlor Aethylsilane (T,c,F,R) 284. 2,!j-Dimethylhexane-2,5-Dihydroxide (F) 285. *l,l-Dimethylhydrazine, UDMH (TJ?) 286. *Dimethyl sulfate, Methyl sulfate (T) \ 287. *Dimethyl sulfide, Methyl sulfide (T.F,R) 288. 2,4Dinitroaniline (T 289. *Dinitrobenzene (0Id 0, meta, para) (T,R) 0- ENVIRONMENTAL HEALTH TITuE22 (p. 1800.62) (R-W S, NO. S-1-1246) 290. Dinitrochlorobenzene, l-Chlor~2,4dinitrobenzene(T,R) 291. +4,&Dinitro-ortho-cresol, DNPC, SINOX, EGFTOL 30 (T) ( 295. *DINOSEB; 296. ( bis (0,Odiethyl phos- horodithioate) T) 298. hpentaerythritoi hexanitrate (R) 299. *Diphenyl, Biphenyl, Phen lbenzene (T) 300. Diphenylamine, DPA, N-8 henylaniline (T) 301. *Diphenylamine chloroarsine, Phenarsazine chloride (T) 302. *Diphen ldichlorosilane (T,C,R) 303. Dipicryr amine, Hexanitrodiphenyl amine (T,R) 304. Dipro yl ether (T,F) 305. *Ddton, DI-SYSTON;O,O-Diethyl S-[2(ethylthio) ethyl] phos- i horodithioate (T 306. bodec ltrichloroJ * me (T,C,R) 307. *DOWJ 0-139, ZEClXAN, Mencarbate, 4 (Dimethylamino)-3,!"e- thy1 henyl methylcarbamate (T) 309. *DdONATE, Fonofos, 0-Ethyl-S-phenyleth 1 phosphonodithioate (T) 310. *Endosulfan, THIODAN; 6,7,8,9,10,1@HexacK ore 1,5,!ja,6,9, Sa-hexah dro-6,9-methane2,4,3-benzo-dioxathiepinde(T) 31 1. *Endoth9 ,7-Oxabicyclo [2.2.l]heptane-2,3dicarbo~ylicacid (T) 312. *Endothion, EXOTHION, S[(5-Methoxy4oxdH-pyran-%yl) -methyl J 0,O-dimethyl phosphorothioate (T) 313. *Endrin; 1,!2,3,4,10,1O-Hexachlor0-6,7-ep0~y-l,4,4,4a,5,6,7,8,8a- octahydro-1,4endo-endo5,gdimethanonaphthalene (T) 314. Epichloroh drin, Chloropro ylene oxide (T,F) 315. *EPN; 0-Ex yl0- ma-nitro Kenyl phenylphosphonothioate (T) - __ 316. *Ethion, NIALAT~;O,O,O',8'-Tetraethyl-S,S-methylenediphos- - -- phorodithioate (T) 317. Ethyl acetate (T,F) 318. Ethyl alcohol, Ethanol (T,F) 319. Ethylamine, Aminoethane (TJ) 320. Ethylbenzene, Phenylethane (T,F) 321. Ethyl butyrate, Ethyl butanoate (F) 322. Ethyl chloride, Chloroethane (Tf) 323. *Ethyl chloroformate, Ethyl chlorocarbonate (T,C,F,R) 324. *Ethyldichloroarsine, Dichloroethylarsine (T,R) 325. *Ethyldichlorosilane (T,C,F,R) 326. *Ethylene cyanohydrin, beta-Hydroxypropionitrile (T,R) 327. Ethylene diamine (T) 328. Ethylene dibromide; l,%Dibromoethane (T) 329. Ethylene dichloride; 1,2-Dichloroethane (T,F) 330. *Ethyleneimine, Aziridine, EI (T,F,R) 331. Ethylene oxide, Epoxyethane (T,F,R) 332. Ethyl ether, Diethyl ether (F,R) I 9- (p. 1800.63) 333 Ethyl formate (T,F 334 'Ethyl mercaptan, E!thanethiol (T,F,R) 335 Ethyl nitrate F,R) 336 Ethylnitrite (f;. 3) 337 *EthvlDhenvldichlorodane (T.c,R).--. 338 E:1 thil'pro *ionate (F) 339 'E Zthyltric 8 orosilane (T,R) 340 'F i ~nsulfothion,BAYER 25141, DMANIT, 0,O-DieLyl-0- l-(methyl- slU Ilfinyl) phenylJ hosphorothioate (T) 341 'F i ?mc arsenate 342 Fi mic chloride, 6)Iron (III) chloride (T,C) 343 'F '(:rrous arsenate, Iron arsenate (T) 344 'F 1uoboric acid, Fluoroboric acid (T,C) 345 F uoride salts (T) 346 'F uorine (T,C,R) 347 'F uoroacetadide, Am, 1082 (T) ( 348 'F uoroacetic acid and salts, Compound 1080 (T) 349 'F uorodonic acid, Fluosulfonic acid (T,C,R) 350 F mnaldehyde, Methanal (T,F) 351 F irmic acid. Methanoic acid (T.C) 352 Fulminate of mercury, Mercuiid cyanate (T,R) 353 TURADAN, NIA 10,242, Carbofuran; 2,3-Dihydro-2,2dimethyl-7-ben- zofuranylmethylcarbamate (T) 354 Furan, Furfuran (T,F,R) 355 Gasoline (F) t 356 'GB, 0-Isopro yl methyl phosphoryl fluoride (T) 357 GlutaraldehyB e (T) 358 Glycerolmonolactate trinitrate R 359 Glycol dinitrate, Eth lene glym! Ltrate (R) 360. Gold fulminate, Go1(r cyanate (R) 361. Guanidine nitrate (F,R) 362. Guanyl nitrosaminoguan lidene hydrazine (R) 363. * Guthion; O,O-Dimethyl-~~~l~3-~~otri~~(4H)-yhethyl Dhomhorodithioate (TI., 364. h&um (F,T,R) 365. *Heptachlor; 1,4,!5,6,7,8,8-Heptachloro4a,4,7,7a-tebahy&d,7-- mehnoindene (T) 366. n-Heptane (and isomers) (T,F) 367. 1-Heptene (and isomers) (T,F) 368. *Hexadecyltrichlorodane (T,C,R) 369. Hexaethyl tetraphosphate, HGlrp (T) 370. Hexafluoro hosphoric acid (T,C) 371. HexamethyP enediamine; l,&Diaminohexane (T) 372. n-Hexane (and isomers) (T,F) 373. 1-Hexene (and isomers) (T,F) 374. n-Hexylamine, 1-Aminohexane (and isomers) (TJ) \ 375. *Hexyltrichlorosilane (T,C,R) 376. 'Hydrazine, Diamine (T,F) 377. Hydrazine azide (T,R) I 9- ENVIRONMENTAL HEALTH TITLE22 (p. 1800.64) (RwW I, NO. 2-4-1246) 378. Hydrazoic acid, Hydrogen azide (T,R , 379. *Hydriodic acid, H dro en iodide (T, d ,R 380. *Hydrobromic acid: Hy%ogen bromide ()r,C,R) 381. *Hydrochloric acid, Hydrogen chloride, Muriatic Acid (T,C,R) 382. *Hydrw anic acid, Hydrogen c anide (T,F,R) 383. *Hydro uoric acid, Hydrogen uoride (T,C,R) 384. Hydrofluosilicicrsy acid, Fluosilicicriy acid (T,C) c 385. Hydrogen peroxide (T,C,F,R) 386. *Hydrogen selenide (T,F) 381. *Hydro ensulfide (T,F) borite compounds (T,c,F,R) 389. In 'um (T) 390. *HrIndiumcompounds (T) 391. Iodine monochloride (TIC$) 392. Isooctane; 2,2,4Trimethylpentane (T,F) 393. Isooctene (mixture of isomers) (F) 394. Isopentane, %Methylbutane (F) 395. Isoprene, %Methyl-1,3-butadiene (T,F,R) 396. Isopropanol, Isopropyl alcohol, %Propanol (T,F) 3W. Isopropyl acetate (T,F) 399. Isopropylamine, %Aminopropane (T,F) 400. Isopropyl 404. 405A. *Kepone; ( 2Hcyclobuta (cd) ntalen$-one, Chlorecone (T) 405B. Lauroyl peroxide, Knddecyl peroxide (T,C,F,R) 406. Lead compounds (T) 407. Lead acetate (T) 408. *Lead arsenate, Lead orthoarsenate (T) 409. *Lead arsenite (T) 410. Lead azide (T,R) 411. Lead carbonate (T) 412. Lead chlorite (T,R) 413. *Lead cyanide (T) 414. Lead 2,4-dinitroresorcinate (T,R) 415. Lead mononitroresorcinate (T,R) 416. Lead nitrate (T,F) 417. Lead oxide (T) 418. Lead styphnate, Lead trinitroresorcinate (T,R) 419. *Lewisite, beta-Chlorovinyldichoroarshe (T) 420. *Lithium (C,F,R) 421. *Lithium aluminum h dride, LAH (C,F,R) 422. *Lithium amide (CJ?5 ) 423. *Lithium ferrosilicon (F,R) 424. *Lithium hydride (C,F,R) 425. *Lithium hypochlorite (T,C,F,R) 426. Lithium peroxide (CJ?,R) .' TITLE!1 2 ENVIR0"TALHEALTH 0- (R.9- 1I 5, NO. kl-lm) (p. 1800.65) 421. Lai ithiumsilicon Fa) 428. *IA ondon purple, tixture of arsenic trioxide, aniline, lime, and ferrous 0Q ride (T) 429. *h1 'agnesium (Fa) 430. *h1 :agnesiwnarsenate (T) 431. *h1 iagnesium arsenite (T) I ! 432. h1 agnesium chlorate (F,R) 433. h1 agnesium nitrate (Fa) 434. h1 :agnesium perchlorate (T,F,R) 435. h1 'a esium roxide, Magnesium dioxide (F) 436. *h1 gc anhyzde (T) 437. h1 'anganese (powder) (F) 438. h1 'anganese acetate (T) 439. *h1 'anganese arsenate, Manganous arsenate (T) 440. h1 anganese bromide, Manganous bromide (T) 441. hA 'anganese chloride, Manganous chloride (T) 442. h1 anganese methylc clopentadienyl tricarbonyl (T) 443. h1 anganese nitrate, Klanganous nitrate (T,F) 444. h1 annitol hexanitrate, Nitrornannite (R) 445. *h1 ECARBAM;O,O-Diethyl S- (N-ethoxycarbonyl N-methylcarbamoyl- na ,ethyl) phosphorodithioate (T) 446. *h1 edinoterb acetate, %tert-Butyl-!j-met.hyl4,6dhitrophenylacetate c1 r) 447. 1: ua-Menthane hydroperoxide, Paramenthane hydroperoxide (F) 448. R1 'ercuric acetate, Mercury acetate (T) 449. h1 'ercuric ammonium chloride, Mercury ammonium chloride (T) 450. hA 'ercuric benzoate, Mercury benzoate (T) 451. h1 :ercuric bromide, Mercury bromide (T) 452. *h4 'ercuric chloride, Mercury chloride (T) 453. *h1 ercuric cyanide, Mercury c anide (T) 454. h1 ercuric iodide, Mercury idde (T) 45!j. h1 'ercuric nitrate, Mercury nitrate (T,F') 456. h1 ercuric oleate, Mer oleate (T) 451. h1 ercuric oxide (red an7 yellow) (T,F) 458. h1 ercuric oxycyanide (TJI) 459. h1 ercuric-potassium iodide, Mayer's reagent (T) 460. h1 ercuric salicylate, salicylated mer (T) 461. h1 'ercuric subsulfate, Mercuric diovzte (T) 462.h1 'ercuric sulfate, Mercury sulfate (T) 463. h1 ercuric thiocyanide, Merc thiocyanate (T) 464. h1 'ercurol, Merc nucleateY ( ) 465. h1 'ercurous bromi Y e (T) 466. hA ercurous gluconate (T) 467. h1 'ercurous iodide (T) 468. hA :ercurous nitrate (T,R) 469. h1 ercurous oxide (T) 470. h1 :ercurous sulfate, Mercury bisulfate (T) 472. *hA [ercury (T) 473. *h1 ercury compounds (T) 9- m0"TALHEALTH TITLE22 (p. lsoo.66) ([email protected], NO. 2--1-12U) 474. Metal carbonyls 475. *Metal hydrides ( 476. Metal powders (TJ? 477A. 'Methomyl, LA"R TE, S-Methyl-N-( (methylcarhatnoyl) oxy) thioacetimidate (T 477B. 'Metho chlor; l,l,l-Tric 1oro-2, %bis (pmethoxyphenyl)ethane, CHEdhRM. MARLATE (TI 478. +Me11 ryethylmercuric chloride, AGALLOL, ARETAN (T) 479. Me1 1 I acetate (TJ?) 480. MetJ , acetone (Mixture of acetone, methyl acetate, and methyl al- cohl C (T,Fk 481. Me11 alco 01, Methanol (TJ?) 482. +Me11 aluminum sesquibromide (F,R) 483. *Me11 aluminum sesquichloride (Fa) 484 Met J amine, Aminomethane (T,F) 485 N-h(I 1 laniline (T) 486 'Met 3 iromide, Bromomethane (T) 487 2M€ yl-1-butene (F) 488 3-Me yl-1-butene (F) 489 Met3 butyl ether (and isomers) (TJ?) 490 Met3 butyrate (and isomers) (TJ?) 491 Met3 chloride, Chloromethane (T,F) 492 .'bMet 3 chloroformate, Methyl chlorocarbonate (T,F,R) 493 'Met 3 chloromethyl ether, CMME (TJ?) 494 Met3 cyclohexane (TJ?) 495 'Met 3 dichloroarsine (T) 496 Wet3b dichlorosilane (T,F,R) 497 *4,4-1 hylene bis (2chloroaniline), MOCA (T) 498. Met 3 ethyl ether (T,F) 499. Met3 ethyl ketone, 2Butanone (T,F) 300. Met3 ethyl ketone peroxide (TJ?) 501. Met3 formate (T,F) 502. *Met3 hydrazine, Monomethyl hydrazine, MMH (T,F) 503. *Met3 isocyanate (T,F) 504. Met3 isopropenyl ketone, 3-Methyl3butene-hne (TJ?) 505. *Met3 magnesium bromide (C,F,R) 506. *Met1 magnesium chloride (C,F,R) 507. *Met1 magnesium iodide (C,F,R) 508. Met3 mercaptan, Methanethiol (TJ? 509. Met1 methacrylate (monomer) (Tb ) 510. *Met3 parathion;O,O-Dimethyl-O-para-nitrophenylphosphorothioate (TI 511. Methyl pro ionate (F) 512. *Methyltrics orosilane (T,C,F,R) 513. Methyl valerate, Methyl pentanoate (and isomers) (F) 514. Methyl vinyl ketone, 3-Butene-%ne (T,F) 515A. 'Mevinphos, PHOSDRIN, 2Carbomethoxy-1-methylvinyldimethyl hosphate (T) 515B. *hex; 1,1~2,3,3~4d~~45b,~D~~8chlor~~y~o-l,3, 4-metheno-1H-cyclobut.a (cd)pentalene, Dechlorane (T) i Ea \ 516. WOW,O-EthylS,Sdipmpyl phosphoroditbioate (T) 517. Molybdenum (powder) (F) 518. Molybdenum trioxide, Molybdenum anhydride (T) 519. Molybdic acid and salts T 520. Monochloroacetic acid, oracetic acid MCA (T,C) 521. Monochloroacetone, Chloroacetone, l-Chlom2propanone (T) 522. acid (T,C) or coal tar origin), Petroleum ether, Petroleum 528. Nickel (powder) (T,F) 529. Nickel acetate (T) 530. Nickel antimonide (T) ( 531. *Nickel arsenate, Nickelous arsenate T) 532. *Nickel carbonyl, Nickel tetracarbonyI (T) 533. Nickel chloride, Nickelous chloride (T) 534. *Nickel cyanide (T) 535. Nickel nitrate, Nickelous nitrate (T,F,R) 536. Nickel selenide (T) 537. Nickel sulfate (T) 538. Nicotine, beta-pyridyl-alpha-N-methylpyrrolidine (T) 539. Nicotine salts (T) ( 540. Nitric acid (T,C,F) 541. Nitroaniline, Nitraniline (ortho, meta, para) (T,R) 542. *Nitrobenzol, Nitrobenzene (T) 543. *4-Nitrobi henyl, 4NBP (T) 544. Nitro car go nitrate (F,R) 515. Nitrocellulose, Cellulose nitrate, Guncotton, Pyroxylin, Collodion, _- Pyroxylin (nitrocellulose) in ether and alcohol (F,R) 546. Nitrochlorobenzene, Chloronitrobenzene (ortho,meta,para) (T) 517. Nitrogen mustard (T,C) 548. Nitrogen tetroxide, Nitrogen dioxide (TJ?) 549. Nitro ycerin,Trinitroglycerin (T,F,R) 550. Nitro8' drochloric acid., Aqua regia (T,C,F) 551. *Nitrop enol (ortho,meta, a) (T) 552. *N-Nitrosodimethylamine,L gethyl (T) 353. Nitrosoguanidine (R) 554. Nitrostarch, Starch nitrate (Fa) 555. Nitroxylol, Nitroxylene, Dimethylnitrobenzene (2,4-$,4-$,Womers) (TI 556. 1-Nonene, 1-Nonylene (and isomers) (T,F) 551. *Nonyltichlorosilane (T,R) 558. *Octadecyltrichlorosilane (T,R) i 559. n-Octane (andisomers) (T,F) 560. I-Octene, 1-Caprylene (T,F) 0- ENVIR0"NTALHEhLTH lTrLE22 (p. laoo.68) (Ikgbtrr RbNa %l*lcI) 561. *OctyltrichlorosiIane (T,R) 563. *Oleum, Fuming sulfuric acid (T,C,R) 565. 0s"com unds (T) 566. Oxalicacid (.F" ) 567. *Oxygen difluoride T,C,R) 568. *Para-oxon, MlNTA L;O,O-Diethyl-O-para-nitrophenyl h hate T) Lo i 569. *Para % on; 5,O-Diethyl-0-para-nitropheayl phoephorothioate (T) 57OA. *Pentaborane (T,F,R) SIOB. Pentachlorophenol, PCP, DOWICIDE 7 (T) 571. Pentaerythnte tetranitrate, Pentaerythritol tetranitrate (R) 572. n-Pentane (andisomers) (T,F) 573. %Pentanone, Methyl propyl ketone (and isomers) (T,F) 574. Peracetic acid, Per0 acetic acid (T,C,F',R) 575. Perchloric acid (T,CY ,R) 576. Perchloroethylene, Tetrachloroeth lene (T) 5T7. *Perchloromethyl merca tan, Tricd oromethylsulfenyl chloride (T) 578. Perchlory1 fluoride (T,8 ,F) 580. Phenol, Carbolic acid (T,C) 581. *Phenyldichloramine (TJ) 582. Phenylenediamine, Diaminobenzene (ortho,meta,para) (T) 583. Phenylh drazine h drochloride (T 584. *Phenylpienol, dozenol, DOWIhE I (T) 585. 'Phenyltrichorosilane (T,R) 586. *Phorate, THIMFT; 0,O-Diethyl-S [ (Ethylthio) methyl] phosphorodi- -l$dithiolane (T) (T,CP,R) 600. *Phosphorus tribromide (T,C,R) 601. *Phosphorus trichloride (T,C,R) 602. Picramide,TrinitToaniline (T,R) 603. Picricacid,Trinibo henol (T,R) 604. Picryl chloride, 2 oro-l,3,5;-trinitrobnzene (T,R) 605. *Platinumcompunds (T) 606. *Polychlorinated biphenyls, PCB, Askarel, AROCLOR, CHLOREX- TOL, INERT", PYRANOL (T) TITLE22 ENVIRONMENTALHEALTH 0- (R.gbt.r Iff NO. b-1-la) (p. lsoo.69) W. Pol yl nitrate F,R W. POZAN; 0,O-&ti 'e yl-0- (4-methylumbellifkrone) phosphorothio- ate (T) 609. *Potassium (C,F,R) 610. *Potassium arsenate T) 611. *Potassium arsenite ((r ) 612. *Potassium bifluoride, Potassium acid fluoride (T,C) 613. Potassium binoxalate, Potassium acid oxalate (T) 614. Potassium bromate (T,F) 615. *Potassium cyanide (T) 616. Potassium dichloroisocyanurate (T,F) 617. Potassium dichromate, Potassium bichromate (T,C,F) 619. Potassium fluoride (T) 620.* Potassium hydride (C,F,R) 621. Potassium hydroxide, Causticpotash (T,C) 622. Potassium nitrate, Saltpeter ( ,R) 623. Potassiumnitrite (F,R) 624. Potassium oxalate (T) 625. Potassium perchlorate (T,F,R 626. Potassium permanganate (T, ,F) 627. Potassium peroxide (C,F,R) 628. Potassiumsulfide (T,F) 629. *Propargyl bromide, $Bromo-1-propyne (T,F) 630. *beta-Pro iolactone, BPL (T) 631. Propionap dehyde, Propanal (T,F) 632. Propionic acid, Propanoic acid (T,C,F) 633. n-Propyl acetate (TJ?) 634. n-Propyl alcohol, I-Propanol (T,F) 635. n-Pro ylamine (and isomers) T,F) m. *PropyP eneimine, SMethyl-Le (T,F) 637. Propylene oxide (T,F) 638. n-Propyl formate (T,F) 639. n-Propyl mercaptan, 1-Propanethiol (T,F) 640. *n-Propyltrichlorosilane (T,C,F,R) 641. *Prothoate, FOSIION, FAC; 0,O-Diethyl-Scarboethoxyethyl phos- horodithioate (T) w.Fyridine (T,F 643. *Pyrosulfuryl c1 oride, I)lsulfuryl chloride (T,C,R) 644. *Quinone; 1,rl-Benzoquinone (T) 64!j. Raney nickel (F) 646. *Schradan, Octamethyl pyrophosphoramide, OMPA (T) 647A. *Selenium (T) 647B. *Selenium com unds (T) . 648. *Selenium fluori8" e (T) 649. *Selenous acid, Selenious acid and salts (T i 650. *Silicon tetrachloride, Silicon chloride (T,J ,R) 651. *Silver acetylide (T,R) 652. Silver azide (T,R) 653. Silver compounds (T) 0- ENVIRONMENTAL HEXLTH TITLE22 (p. 1800.70) (R-b N, NO. hl-lUr) 64. Silver nitrate (T) 6!5!5. Silver styphnate, Silver trinitroresorcinate (T,R) c 656. Silver tetrazene (T,R) 657. *Sodium (C,F,R) (3%. Sodium aluminate (C) 659. *Sodium aluminum hydride (C,F,R) 660. *Sodium amide, Sodamide (C,F,R) ( 661. *Sodium arsenate (T) 662. *Sodiumarsenite (T) 663. Sodium azide (T,R) 664. *Sodium bifluoride, Sodium acid fluoride (T,C) 665. Sodium bromate (T,F) 666. *Sodium cacodylate, Sodium dimethylarsenate (T) 667. Sodium carbonate peroxide (F) 668. Sodium chlorate (T,F) 669. Sodium chlorite (T,F) 670. Sodium chromate (T,C) 671. *Sodimcyanide (T) 672. Sodium dichloroisocyanurate (F 673. Sodium dichromate, Sodium bic kromate (T,C,F) 674. Sodium fluoride (T) 675. *Sodium hydride (T,C,F,R) 676. Sodium hydrosulfite, Sodium hyposulfite (F) 677. Sodium hydroxide, Caustic soda, Lye (T,C) 678. *Sodium hypochlorite (T,F,R) 679. *Sodium methylate, Sodium methoxide (C,F,R) 680. Sodiummolybdate (T) 681. sodium nitrate, soda niter (T,F,R) 682. Sodium nitrite (T,F,R) 683. Sodium oxide, Sodium monoxide (T,C) 684. Sodium perchlorate (T,F,R) 685. Sodium permanganate (T,F) 686. *Sodium peroxide (T,F,R) 681. sodium picramate (T,F,R) 688. *Sodium potassium alloy, NaK,Nack (C,F,R) 689. *Sodium selenate (T) 690. Sodium sulfide, Sodium hydrosulfide (T,F) 691. Sodium thiocyanate, Sodium docyanate (T) 692. Stannic chloride, Tin tetrachloride (T,C) 693. *Strontium arsenate (T) 694. Strontium nitrate (T,F,R) 69!j. Strontium peroxide, Strontium dioxide (F,R) 696. *Strychnine and salts (T) 697. Styrene,Vin lbenzene (T,F) 698. Succinic aci (r peroxide (T,F) 6!B. Sulfide salts (soluble) (T) I 700. *Sulfotepp, DITHIONE, BLADAFUM, Tetraethyl dithiopyrophos- hate, TEDP (T) 701. !ulfur chloride, Sulfur monochloride (T,C,R) _- --. n ia I m 0- ENVIRONMENTAL HEALTH TITLE22 (p. 1800.72) (R.gi8t.r a NO. %l-l=) 744. Trichloroethylene; Trichlorethene (T) ( 745. Trichloroisocyanuric acid (TJ,F) 746. *!2,4~Tnchlorophenoxyaceticacid; !2,4,5T (T) 747. Trichlorosilane, Silicochlorofonn (T,C,F,R) 748. Trimethylamine,TMA (T,F) 749. Trinitroanisole; 2,4,6-Trinitro henyl methyl ether (T,R) ( 750. 1,3$Trinitrobenzene,TNB (f;. ,R) 751. 2,4,6-Trinitrobenzoic acid (T,R) 752. Trinitronaphthalene, Na htite (T,R) 733. !2,4,6-Trinitroresorcinol, J)typhnic acid (T,R) 754. !2,4,6Trinitrotoluene, TNT (T,F,R) 7%. *tris (I-Aziridinyl) phosphine oxide, Triethylenephosphoramide, TEPA (T) 756. Tungstic acid and salts (T) 757. Turpentine (T,F) 758. Uranyl nitrate, Uranium nitrate (T,F,R) ( 759. Urea nitrate (T,F,R) 760. n-Valeraldehyde, n-Pentanal (and isomers) (T,F) 761. Vanadic acid salts T) 762. Vanadium oxytrichi oride (T,C) 763. *Vanadium pentoxide, Vanadic acid anhydride (T) 764. Vanadium tetrachloride (T,C) 765. Vanadium tetraoxide (T) 766. Vanadium trioxide, Vanadium sesquioxide (T) 767. Vanadyl date, Vanadium sulfate (T) 768. Vinyl acetate (F,T) 7@. *Vinyl chloride (T,F) i 770. Vinyl ethyl ether (F) 771. Vinylidene chloride, VC (T,F) 772. Vinyl iso ropy1 ether (F) 773. *Vinyltricli orosilane (T,C,F,R) 774. VX, 0-Ethyl methyl phosphoryl N,N-diisopropyl thiocholine (T) 775. *wEPSYN 155, WP 155, Triamiphos, a-(5-Amino-3- henyl-lH-l,2,4- triazol-1-yl)-N,N,N',N'-tetramethyl pR" osqhonic diamia e (T) 776. Xylene, Dimethylbenzene (orthometqpara) (T,F) 777. Zinc (powder) (F) 778. Zinc ammonium nitrate (T,F) 779. *Zinc arsenate (T) 780. *Zincarsenite (T) 781. Zinc chloride (T,C) 782. Zinc compounds (T) 783. *Zinc cyanide (T) 784. Zincnitrate (T,F,R) 785. Zincpermanganate T,F) 786. Zinc peroxide, Zinc 'oxide (T,F,R) 787. *Zinc phosphide (T,F,R)61 788. Zincsulfate (T) 789. Zirconium ( wder) (F) 790. *Zirconium c oride, Zirconium tetrachloride (T,C,R) 791. Zirconium picramateI? (F) I (e) List of Common Names. In this subsection a dagger denotes the cam- mon name of a waste which comes under the provisions of this chapter if it contains a hazardous material. Acetylene sludge (C) Acid and water (C) Acidsludge (C) AFUFloc (T) Alkalinecausticli uids (C) Alkaline cleaner (I ) Alkaline corrosive battery fluid (C) Alkaline corrosive liquids (C) Asbestos waste (T) Ashes (T,C) Bag house wastesf Batteryacid (C) i Beryllium waste (T) Bil e water (T) Bo{ er cleaning waste (T,C) Bunker Oil (T,F) Catalystt Causticsludge (C) Caustic wastewater (C) Chemical cleanersf Chemical toilet wastef Cleaning solvents (F) i Corrosion inhibitor T,C) Data processing flui6 (F) Drilling fluidsf Drilling mudf Dyest Etching acid liquid or solvent (CJ?) Fly ash (T,C) Fuel waste (T,F) Insecticides (T) Laboratory wastef Lime and sulfur sludge (C) Lime and water (C) Limesludge (C) Lime wastewater (C) Liquid cementf Liquid cleaning compoundsf Mine tailings Obsolete exp tosives (R) Oil and water (T) Oil Ash (T,C) Paint or varnish) remover or stripper (F) Paint Ler(Ty) Paint waste (or slops) (T,F) .. . \ I' ..... - . .. . a- Pickling liquor (C) Pigmentst ,. . Plating waste (T,C) . . ., Printing Inkt ... '. .. .. : . Spent aci (C) Spent caustic (C) Spent (or waste) cyanide solutions (T,C) Spent mixed acid (C) Spent plating solution (T,C) Spent sulfuric acid (C Stri ping solution (T,B ) S&nation oil (F) Tank bottom sediment1 Unrinsed ticide containers (T) Unwant or waste pesticides--an unusable portion of active ingredient or undiluted erformulation (T) Waste chemicalst Waste expolridest Waste (or do ) oil (T) i weed mer R, NOTE: Autbority cited: sections 208,25141 and e5130, Health and safety Code. Refer- ence: Sections 25140 and 25141, Health and Safety Code. HISLY)RY: 1. Amendment filed 927434; effective thirtieth day thereafter (Register 84, No. 41). SL Editorial correction of subsection (d) and NOTE filed 1cF38d; designated effective 10.e7-84 (Register 84, No. 41) Article 10. Extremely Hazardous Wastes and Extremely Hazardous Materials < 6SS. List of Extremely Hazardous Wastes. NOTE: Autbority cited: Sections eoQ, 25141 and 23150, Health and Safety Code. Refer- ence: Section 25141, Health and safety Code. HISI'ORY 1. Repealer of Article 10 (Section 666R5) filed 9-2184; effective thirtieth day thereafter (Register 84, No. 41). I " o= ENVIRONMENTAL HEALTH TITLES (P* 1793) (Rogbtu u No, &+.a) .. 66X6. clusificrtion of (I Waste u H.ludous or Nonhazardous...... (a) A waste must be clasi6ed a hazardous waste it is within the scope of .. if -. Section 663a) and (1) it is hazardous pursuant to any criterion of Article 11, or (2) it otherwise meek the definition of a hazardous waste in Section 23117 of the Health and Safety Code, and no rson shall deviate from the provisions ( of this Chapter in the management or a hazardous waste, except as provided for in subsection e) of this section or Section 66310. (b) It shall be 6e waste producer's responsibility to detennine if the waste is classified as a hazardous waste pursuant to Section m(a). If the producer determines that the waste is hazardous, the waste shall be managed pursuant to the provisions of this Chapter. If the producer determines that the waste is nonhazardous, the producer, except as provided for in Section 663E(e),may either proceed to manage the waste as nonhazardous or apply to the Depart- ment for concurrence with the nonhazardous determination through the notifi- cation procedure set forth in Section oS(c)before managing the waste as nonhazardous. (' (c) If the waste producer chooses to obtain departmental concurrence with the nonhazardous waste determination, notification to the Department shall be on the Waste Cbdication Form provided by the Department on which the producer shall set forth all information required by Article 11. Pendmg concur- -rence by the Department ursuant to Section 663&(d) or (g), the producer shall manage the waste as R azardous waste. (d) The Department, within 30 calendar days of receipt of a notification pursuant to Section 663O!j(c), shall acknowled e in writing receipt of the notifi- cation. The waste producer, after receipt of tBe acknowledgement, may man- ( age the waste as nonhazardous unless the Department, in conjunction with the acknowledgement, notifies the producer that classification of the waste as non- hazardous is disapproved or that the information submitted by the producer is incomplete or inad uate and what additional information will be needed. (e) If a waste pr3 ucer wishes to c)assify and manage as nonhazardous a waste which is hazardous by a criterion of Article 11, or is of a kind or from a source listed in 40 CFR 261.31,261.32, 261.33(e) or 261.33(f), codified July 1, 1982, because it has mitigating hysical or chemical characteristics which rend- cant as a hazard toR uman health and safety, livestock, and wildlife, erthe it pr ucer shall appl to the De artment fcr its approval to classify and managehP the waste as no dous. ?%eap lication for approval shall be on the Waste Classification Fokrovided by $e Department. The Department within 30 calendar days of receipt of the application, shall acknowledge & writing receipt of the application and that the a plication is com lete, or that the application is incomplete or inadequate an s what additionaf information will be needed. Pending written approval by the De artment, the waste re ducer shall manage the waste as hazardous waste. 4e Department sdap prove or disapprove in writing classification and management of the waste as nonhazardous within 60 calendar days of receipt of the complete application. TITLE22 ENVIRONMENTAL HEALTH 4 66315 (Roghtw m No. W-1 (p. 1792.3) t (d) The Department shall within 60 calendar days after receipt of a com- plete application for a variance pursuant to Section 66310 (a) inform the appli- cant in writing that the variance is granted or denied, unless the Department must rely on another public or private enti for all or part of the processing of the application and the delay is caused by t other entity. If the application I is incomplete, the Department shall withinL 60 calendar days after its receipt notify the applicant in writin what further information is needed in order that the ap lication may be resu (3mitted in a com lete form. (e) he Department may ant a variance R om the provisions of this chap- ter to allow use of a test met I? od or analytical method alternative to that pre- scribed in Article 11 for use in classifyin a specific waste. For the variance to be granted, the applicant must show to ta e satisfaction of the Department that the roposed alternative test method or analytical method is equal or superior to e appropriate corresponding method in Article 11, when applied to the specifictK waste with respect to accuracy, precision, sensitivity and stringen . ( (f) An ap lication for a variance pursuant to Section 66310(e) shall inclu7 e all of the folY owing: (1) The name and address of the producer of the waste and where the waste is located. (2) A complete description of the waste, including its composition and source or process of generation. (3) A complete description of the proposed alternative test method or ana- lytical method, including all equipment and procedural steps used. (4) A comparison of results obtained from a statistically signtficant number of replicate trials with the proposed alternative test method or analytical \ method with those results obtained from use of the appropriate corresponding method prescribed in Article 11 when both methods are applied simultaneously to the applicant’s waste. (5) An assessment of any factors which might interfere with or limit the applicability of the pro sed test method or analytical method. (6) A description oft‘Ep e quality control and quality assurance procedures to - .- be followed to ensure the accuracy, precision, sensitivity and stringency of the proposed test method or analytical method. (g) The Department shall within 60 calendar days after receipt of an applica- tion for a variance ursuant to Section 6631O(e) notify the applicant that the a plication is compP ete and accepted for rocessing by the Department or that t Ke application is incomplete and what Purther information is r (h) The Department shall within 180 calendar days of receipt ”4”i’”d.o a complete for a variance pursuant to Section 66310(e) notify the applicant that for a variance is granted or denied. variance requested pursuant to Section 66310(a) (I), (a) 2), or (e) Department shall provide to the applicant in writing 6e reason for the denial. NOTE: Authority cited: Sections 208, 25141 and 25150, Health and Safety Code. Refer- ence: Section 25141, Health and Safety Code. \ HISTORY: 1. Amendment filed 9-27-84; effective thirtieth day thereafter (Register 84, No. 41). 66315. Other Requirements. No local a ency shall enforce any requirement, other than those in this chapter, whica would impede interstate or intrastate transportation or -4 I of hazardous waste or which would impede use of facilities for regional multi- county management of hazardous waste. .. . I- 1: . .. TITLE= ENVIRONMENTAL HEALTH 0 66510 (R.gW mb No. %l-lm) (p. 1800.85) . 66505. Operation Requirements for Producer. NOTE: Authority cited: Sections e08,231!50 and 25139, Health and Snfety Code. Refer- ence: Sections e5130 and e5158, Health and safety Code. HISIY)RY: 1. Repealer filed 14-85; effective thirtieth day thereafter (Register 83, No. 2). ( 66!jO8. Accumulation Time for the Generator. (a) A generator may accumulate hazardous waste on site for 90 days or less without a permit or without having interim status provided that: (1) The waste is placed in containers and the generator complies with Arti- cle 24 as it applies to interim status facilities, or the waste is placed in tanks and the generator complies with Article 25 as it applies to interim status facilities except for Section 67258. (2) The date upon which each’period of accumulation begins Q clearly marked and visible for inspection on each container. (3) While being accumulated on site, each container and tank is labeled or marked clearly with the words, “Hazardous Waste”, and the additional lan- guage as required under subsection (c) of this section. (4) The generator complies with the requirements for owners or operators in Articles 19 and 20 and Section 67105. (b) A generator who accumulates hazardous waste for more than 90 days is an operator of a storage facility and is subject to the requirements of Articles 17 through 32 and the permit requirements of Article 6 unless he has been anted an extension to the %May period. Such extension may be granted by geDepartment if hazardous wastes must remain on site for longer than 90 days due to unforeseen, tem rary and uncontrollable circumstances. An extension of u to 30 days may granted at the discretion of the Department on a case-% y-casebasis. (c) A label shall be maintained on all nonstationary containers in which hazardous wastes are stored. Labels shall include the following information: (1) Composition and physical state of the waste. (2) Statement or statements which call attention to the particular hazardous properties of the waste (e. ., flammable, reactive, etc.). (3) Name and address of the person producing the waste. NOTE:Authority cited: Section 208, Health and Safety Code. Reference: Sections 25159 and 25159.5, Health and Safety Code. HISTORY: 1. New section filed 1585; effective thirtieth day thereafter (Register 85, No. 2). 66510. Operation Requirements for Hauler. NOTE: Authority cited: Sections 208, 25150 and 8159, Health and Safety Code. Refer- ence: Sections 25150 and 25159, Health and Safety Code. HISTORY: 1. Amendment of subsection (a) filed 510-79; effective thirtieth day thereafter (Regis- ter 79, No. 19). 2. Amendment filed 10-6-81 as an emergency; effective upon filing (Register 81, No. 42). A Certificate of Compliance must be transmitted to OAL within 120 days or i‘~ emergency language will be repealed on 2-3-82. 3. Certificate of Compliance including amendment of subsection (h) transmitted to OAL 2282 and filed 3882 (Register 8!& No. 11). 4. Renumbering and amendment of Section 66510 to Section W filed 1-3-85;effec- tive thirtieth day thereafter (Register 85, No. 2). i .. . ,... (' 0 66471 ENVIRONMENTAL HEALTH TITLE22 (p. Isoo.40) (Rqtirtu (la Na -1 (d) An owner or operator who initiates a shipment of hazardous waste from (. a treatment, storage or dispod facility shall comply with the generator stand- ards established in this article. (e) This article does not apply to generators handling only hazardous waste produced incidental to owning and maintaining their own place of residence (e.g., household hazardous waste is exempt). ( NOTE: Authority cited: Section 208, Health and Safety Code. Reference: Sections 25139 and 25159.3, Health and Safety Code. HISTORY: 1. Repealer and new section filed 1-3-85; ektivethirtieth day thereafter (Register 83, No. 2). 66471. Haziudous Waste Determination R uirement for the Generator. A person who generates a waste, as defin3 in the Health and safety Code, Sections 25122 and 25122.5, shall determine if that waste is a hazardous waste using the following method: (a) He shall determine if the waste is listed as a hazardous waste in Article ( 9 or 11. (b) If the waste is not listed as a hazardous waste in Article 9 or 11, he shall determine whether the waste is identified in Article 11 by either: (1) Testing the waste according to the methods set forth in Article 11, or according to an equivalent method approved by the Department; or (2) Applying knowledge of the hazard characteristics of the waste in light of the materials or the processes used and the criteria established in Article 11. NOTE: Authority cited: Section 208, Health and Safety Code. Reference: Sections e5159 and 251596, Health and Safety Code. HISrORY: ( 1. New section filed 14-85; effective thirtieth day thereafter (Register 85, No. 2). 6647Z EPA Identification Numbers for the Generator. (a) Any generator of hazardous waste shall apply for and receive an EPA identification number. (b) A generator who has not received an EPA identification number may obtain one by applying to the Department. (c) A generator shall not offer his hazardous waste to tr rters or to treatment, storage or *sal facilities that have not received Tan A identifi- cation number. , (d) A generator shall not treat, store or dispose of, tr rt or offer for trans rtation hazardous waste without having received anT E A identification numE r. NOTE. Authority cited: Section 208, Health and Safety Code. Reference: Sections 25139 and 25159.5, Health and Safety Code. HISTORY: 1. New section filed 14-85; effective thirtieth day thereafter (Register 85, No. 2). TITLE22 ENVIRONMENTAL HEALTH 0- (Rwkt~IL NO.&t*t246) (p. 1800.77) Calculated oral or dermal LD#, = -100 n %Ax- ZT x=l Ax where%Ax is the weight percent of each component in the waste mixture and Th is the acute oral or dermal IDsoor the acute oral LDm of each component. NOTE: Authority cited: Sections 208,25141 and 25150, Health and safety Code. Refer- ence: Section 25141, Health and Safety Code. HIWRY: 1. Editorial correction filed lW-84;designated effective 10-21-84 (Register 84, No. 41). 66699. Persistent and Bioaccumulative Toxic Substance. (a) Any waste is a hazardous waste which contains a substance listed in subsections (b) or (c) of this section: i (1) at a concentration in milligrams per liter as determined pursuant to Section 66700 which ex& its listed soluble threshold limit concentration, or 2) at a concentration in milligrams per kilogram in the waste which exceeds its ted total threshold limit concentration. Is(b) List of Inorganic Persistent and Bioaccumdative Toxic Substances and Their Soluble Threshold Limit Concentration (SIZC) and Total Threshold Limit Concentration ('ITLC) Values. substance Antimony andlor antimony compounds...... 15 Arsenic andlor arsenic compounds ...... 5.0 Asbestos ...... - Barium and/or barium compounds (excluding bar- ite) ...... 100 Beryllium and/or beryllium compounds...... 0.75 Cadmium andlor cadmium compounds ...... 1.0 Chromium (VI) compounds ...... 5 Chromium andlor chromium (111) compounds ...... !j60 Cobalt andlor cobalt compounds ...... 80 Copper and/or copper compounds ...... 25 Fluoride salts ...... 180 Lead andlor lead compounds ...... 5.0 Mercury andlor mercury compounds ...... 0.2 Molybdenum and/or molybdenum compounds ...... 350 Nickel andlor nickel compounds ...... 20 Selenium andlor selenium compounds...... 1.o Silver and/or silver qompounds ...... 5 Thallium andlor thallium compounds...... 7.0 Vanadium andlor vanadium compounds ...... 24 Zinc andlor zinc compounds...... 250 * SIZC and TTLC values are calculated on the concentrations of the ele- ments, not the compounds. f In the case of asbestos and elemental metals, a plies onl if the are in a friable, powdered or fine1 divided state. As&stos inc!udes cLsotile, i amosite, crocidolite, tremoi 'te, anthophyllite, and actinolite. tt Excludinn barium sulfate. 0" ENVIRONMENTAL HEALTH TITLE22 (p. 1800.78) (R-h I,NO. bl-Iu6) (c) List of Organic Persistent and Bioaccumulative Toxic Substances and Their Soluble Threshold Limit Concentration (STLC) and Total Threshold Limit Concentration ('ITLC) Values. slzc Tnc Wet Weight substanm mg/l mg/k Aldrin ...... 0.14 1.4 chlordan ...... 025 2.5 DDT, DDE, DDD ...... 0.1 1.0 %,CDichlorophenoxyaceticacid ...... 10 100 Dieldrin ...... 0.8 8.0 Dioxin (2,3,7,&n=DD)...... 0.001 0.01 Endrin ...... 0.m 0.2 Heptachlor ...... 0.47 4.7 Kepone ...... 2.1 21 Lead compounds, organic ...... - 13 Lindane ...... 0.4 4.0 Methoxychlor ...... 10 100 Mirex ...... 21 21 Pentachlorophenol ...... 1.7 17 Polychlorinated biphenyls (PCBs) ...... 5.0 50 Toxaphene ...... 0.5 5 Wchloroethylene ...... 204 %M 2,4,5-Trichlorophenoxypropionic acid ...... 1.o 10 NOTE: Authority cited: Sections 208,25141 and 25150, Health and Safety Code. Refer- ence: Section 25141, Health and Safety Code. HEXORY: 1. Editorial correction filed 10-5-84; designated efkctive 10-21-84 (Register 84, No. 41). 6670. Waste Extraction Test (m). (a) The WET described in this section shall be used to determine the amount of extractable substance in a waste or other material as set forth in Section 66699 (a) c- - (b) E&pt as provided in Section 66100(d)$the wET.W be carried out ifL the tod concentration in the waste, or other miiterial, bf any substanm listed in Section 66699-equalsor ex4the SIZC value, but does not exceed the 3TLC value, given for that substance. The total concentrations of substances i listed in Section 66699 shall be determined by analysis of samples of wastes, or other materials, which have been prepared, or meet the conditions, for analysis as set forth in subsections (c and (d) of this section. Methods used for analysis for total concentrations of su bstances listed in Section 66699 shall be those given in the following documents or alternate methods that have been approved by the De artment pursuant to Section 66310(e): (1) for metal elements and their com unds, the waste shall be digested according to the indicated methods descri& in "Test Methods for Evaluating Solid Waste, PhysicalIChemical Methods", SW-846,hd edition, U.S. Environ- mental Protection Agency, 1982: . .. < '. TITLE 22' ENVIRONMENTAL HEALTH $66742 (Rogi8hr 16. No. 10-4446) (p. 1800.84.1) 66740. List of Special Wastes. (a) The following is a noninclusive list of wastes which shall be classifiable as special wastes pursuant to Section 66744 provided they meet the criteria and requirements of Section 66742: (1) Ash from burning of fossil fuels, biomass and other combustible materials. \ (2) Auto shredder waste. (3) Baghouse and scrubber wastes from air pollution control. (4) Catalyst from %oleum refining and chemical plant processes. (5) Cement kiln rust. (6) Dewatered sludge from treatment of industrial process water. (7) Dewatered tannery sludge. (8) Drilling mud from drillin of gas and oil wells. (9) Refractory from industriaf fumances, kilns and ovens. (10) Sand from sandblasting. (11) Sand from foundry casting. (12) Sla from coal gasification. (13) Sufur dioxide scrubber waste from flue gas emission control in combus- tion of fossil fuels. (14) Tailings from the extraction, beneficiation and processing of ores and minerals. NOTE: Authority cited: Sections 208,25140,25143 and 25150, Health and Safety Code. Reference: Sections 25117,25140 and 25143, Health and Safety Code. HISTORY: 1. New section filed 43085;effective thirtieth day thereafter (Register 85, No. 18). 66742. Criteria and Requirements of a Special Waste. (a A waste which meets all of the following criteria and requirements may be cI assified as a special waste ursuant to Section 66744: (1) It is a solid, a water-basef; sludge or a water-based slurry, of which the solid constituents are substantially insoluble in water. (2) It is a hazardous waste only because: (A) It contains a persistent or bioaccumulative substance listed in Section 66699(b) at a solubilized and extractable concentration exceeding its Soluble Threshold Limit Concentration (SIZC), or at a total concentration exceedin its Tota! Threshold Limit Concentration 'ITLC), as said STLC and 'ITL 8 values are set forth in Section 66699(b) and 6etermined as prescribed in Section 66700;except that 1. It shall contain no persistent or bioaccumulative substance listed in Section 66699(b) at a solubilized and extractable concentration in milligrams per kilo- gram of waste exceeding the lTLC value for the substance as set forth in Section 66699(b) and determined as prescribed in Section 66700;and 2. It shall contain no persistent or bioaccumulative inor anic substance listed in Section 66723 (b) at a concentration equal to or excee%ng the TTLC value of the substance as set forth in Section 6fj723(b). (b) Special wastes do not include wastes which: (1) Are hazardous wastes pursuant to or because of: (A) Any criterion of a hazardous waste or other provision set forth in Section =%(a) (11, (a) (2), (a) (3), (a) (4), (a) (5), (a) (71, and 6);section 66702; Section 66705;and Section 66'708; or (B) Any criterion of an extremely hazardous waste or other provision set forth in Section 66720 and Section 66723; or om44 ENVIRONMENTAL HEALTH TITLE22 (p. 1800.842) (Rogirtn No. 1erWr) (C) Any constituent which is a substance or material not listed in Section (- =(a) (5) or Section 66699 which experience or testing has shown to pose a threat to human health or the environment because of its carcinogenicity, chronic toxicity, bioaccumulative properties or persistence in the environment; or (D) The characteristic of EP toxicity, as this characteristic is set forth in 40 CFR 261.24 (revised as of July 1,1982) except for wastes which are exempted ( or delisted under 40 CFR, Sections 260.22,261.4(b),261.5,261.6 (Revised as of July 1,1982);or (2) Contain any of the following: (A) More than 1.0 rcent by weight of any organic substance or mixture of organic substance wRf 'ch is acutely toxic pursuant to Section =(a) (l), (a)@)or W3) or (B) More than 0.1 percent by weight of an organic substance or mixture of organic substance which is extremely hazar Bous pursuant to Section 66680 or &cticm %'EZO(a) (l), (a) (2), a) (3 or (a) (4); or (C) Any organic substance Ldte in Section 66699(c) at a total concentration exceeding the STLC value given for that substance; or (D) An~inorganicor or anic material which is extraneous to the waste as it is norm y roduced by t fl e producer of the waste, excepting material which are incidentar to, or necessary for, the handling of the waste. (3) Are hazardous wastes for which there are land @sal restrictions pur- suant to Article 15. NOTE: Authority cited: Sections 208,25141,25143 and 25150, Health and Safety Code. Reference: Sections 25117 and 25143, Health and Safety Code. HISTORY: 1. New section filed 44045;effective thirtieth day thereafter (Register 85, No. 18). 66'744. Classification of a Waste as a Special Waste. (a) A enerator who wishes to classify and mana e the waste as a special waste sh s obtain the prior written approval from ke Department for such classification and management. The application for approval shall provide all the following information: (1) The name and address of the generator and the address where the waste is produced and located. (2) A description of the waste which shall include its source, physical state, and rate of generation. ( (3) hemical analysis data showing that the waste meets the requisites of a special waste pursuant to Section 6674!2(a)(2). (4) Chemical analysis data, chemical and hysical test data, and bioassay data, or factual information on the origin of tRe waste, which establish that it meets the criteria and requirements of special wastes in Section 66742(a) (1) and Section 66742(b). (b) For wastes which are continuously or repetitively enerated at the same facility, from the same process, utilizing the same kin s of materials (with respect to origin, composition and roperties) the requirements of this section can be met by the submission oP the required information either for each separately enerated quantity of the waste or for a representative sample of the continuousP y or repetitively generated waste. NOTE Authority cited: Sections 208,25143 and 25150, Health and Safety Code. Refer- ence: Section 25143, Health and Safety Code. HISTORY: I 1. New section filed 4-30-85; effective thirtieth day thereafter. (Register 8!5, No. 18). TITLE22 ENVIRONMENTAL HEALTH 0- (R-i~tw 86, NO. 27-7+86) (p. 1800.95) 66898. Applicability of Other Requirements of This Chapter. Nothing in this article shall be construed to relieve a person from handlin and managing a chemical toilet waste as a hazardous waste in accordance wit i the requirements of this chapter if the chemical toilet waste contains a hazard- ous material or is a hazardous waste as defined in Sections 66084 and 66088, respectively, or is listed in either Section 66680 or Section 66685 of this chapter except that a person who produces, hauls, or dis ses of chemical toilet waste shall be exempt from the requirements of Articp" es 2 and 4 through 10 of this chapter if disposal of the waste is in accordance with the requirements of Chapter 6, Division 20, Health and Safety Code and Article 3, Chapter 1, Divi- sion 7.5, Water Code. NOTE: Authority and reference cited: Section 208, Health and Safety Code. HISTORY: 1. Amendment filed 510-79; effective thirtieth day thereafter (Register 79, No. 19). Article 15. Land Disposal Restrictions 66900. List of Restricted Hazardous Wastes. The following hazardous wastes are subject to the restrictions specified in this article: (a) Liquid hazardous wastes containing free cyanides at concentrations greater than or equal to loo0 mgll. (b) Liquid hazardous wastes containing the following dissolved metals (or elements) or compounds of these metals (or elements) at concentrations great- er than or equal to those specified below: Arsenic and/or compounds (as As) 500 mgll Cadmium and/or compounds (as Cd) 100 mgll Chromium (VI) and/or compounds (as Cr+VI) 500 mgll Lead andlor compounds (as Pb) 500 mgll Mercury andlor compounds (as Hg) 20 mgll Nickel and/or compounds as Ni) 134 mgll Selenium and/or compoun6 s (as Se) 100 mgll Thallium andlor compounds (as Th) 130 mgll (c) Liquid hazardous wastes having a pH less than or equal to two (2.0). (d) Liquid hazardous wastes containing olychlorinated biphenyls at con- centrations greater than or equal to 50 mglP. (e) Hazardous wastes containing halogenated organic compounds in total concentration greater than or equal to loo0 mg/kg. NOTE: Authority cited: Sections 208, 25150 and 25159, Health and Safety Code. Refer- ence: Sections 25140,25150,25159 and 25159.5, Health and Safety Code. HISTORY: 1. New Article 15 (Sections 669OMS935,not consecutive) filed 12-23-82, effective thir- tieth day thereafter (Register 82, No. 52). 2. Editorial correction of subsections (a) and (b) filed 12-28-82 (Register 82, No. 52). 66905. Land Disposal Restrictions and Schedule. i (a) On and after each restriction date listed below, no person shall use any land di sal method for the specified restricted hazardous wastes, except as provide?r in this section and Sections 66910 through 66935. (1) June 1, 19kyanide wastes as described in Section 66W(a). (2) January 1,1984-toxic metal wastes as described in Section 66900 b);acid wastes as described in Section 66WO(c); and polychlorinated biphenyi s as de- scribed in Section 66900 (d). 0 66910 ENVIRONMENT, HE LTH TITLE22 (p. 1800.96) (Rogi8t.r 86, No. 27-7a) f (3) January 1, 198!j-liquid wastes containing halogenated organic com- pounds as described in Section 66900 (e). (4) July 8,1987-organic sludges and solids containing halogenated organic compounds as described in Section 669OO(e). (b) At least sixty 60) days prior to each restriction date listed above, the Department shall m e a determination as to whether sufficient recycling and ( treatment capacity willI be permitted and fully operational in the State on the date of the restriction to process substantially all of the hazardous wastes to be restricted from land dis sal on the restriction date. In making this determina- tion, the Department sr all solicit public comments and hold a public hearing at least seventy-five (75) days prior to each restriction date and shall consider, but shall not be limited to, the following: (1) The technical feasibility of the recycling or treatment processes to proc- ess substantially all of the restricted hazardous wastes subject to the restriction; (2) The proximity of the recyclin or treatment processes to generators of the restricted hazardous wastes; anB (3) The technical and economic feasibility of waste reduction, recycling, or treatment of the restricted hazardous wastes at the point of generation. (c) If the Department determines that processes will not be available to recycle or treat substantially all of the restricted hazardous wastes in a particu- lar category, the Department shall revise the restriction date pursuant to the Government Code (Sections 11340, et seq.) in order that restrictions will not become effective prior to the availability of such processes. (d) The Department shall notify all hazardous waste recycling, treatment, stora e, and disposal facility operators by letter within fifteen days after the date as been revised and shall publish a notice in the California Administrative ( Notice Register. NOTE: Authority cited: Sections 208,25150 and 25159, Health and Safety Code. Refer- ence: Sections 25150,25159 and 25159.5, Health and Safety Code. HISTORY: 1. Editorial correction of subsections (b), (c) and (d) filed 12-28-82 (Register 82, No. 52). 2. Amendment of subsection (a) (4) filed 7-285; effective on filing pursuant to Govern- ment Code Section 11346.2(d) (Register 85, No. 27). W10. Land Disposal of Lab Packs Containing Restricted Hazardous Wastes. Small containers of listed restricted hazardous wastes in lab packs ma be ( laced in a landfill until the restriction date in Section 66905(a) (4), dthe Following requirements are met: (a) Restricted hazardous waste shall be ackaged in inside containers which are non-leaking, tightly and securely seale , and of a design and constructed of a material that will not react dangerously with,B be decomposed by, or be i by the waste held therein. The inside containers shall be of the size an redtype specified in the Department of Transportation (DOT) hazardous materials regulations (49 CFR Parts 173 and 178, Subparts A and B as they existed on 17 November 1981), if those regulations specify a particular inside container for the waste. (b) The inside containers shall be overpacked in an open head DOT-s ecifi- cation steel shipping container (49 CFR Part 178, Subpart D, as it elcistea on 17 November 1981) of no more than 110 gallon capacity and surrounded by, at a minimum, a sufficient uantity of absorbent material to completely absorb all of the li uid contents o9 the inside containers. The metal outer container shall be full Bq ter packing with inside containers and absorbent materials. (c) The absorbent material used shall not be capable of reacting dangerously 0 66310 ENVIR0"TALHEALTH TITLE22 (P- (R.ei.awcreyaa4-8m) (k) Not later than 60 calendar days after recei t of an adequate notification (. or application under Section 66NS(c) or (e), tRe Department may request representative samples of wastes which the producer of the waste shall main- tain for that period of time. The quantity of sample submitted shall be adequate to conduct verification tests. (I) Ifa producer's waste changes so that the prior notification or application ( as nonhazardous no longer adequately assesses the waste b the criteria which may render it hazardous, the producer shall then manage Ie waste as hazard- OUS. NOTE: Authority cited: Sections ao8.25141 and eSl50, Health and Safety code. Rekr- e= Section 25141, Health and Saf'ety Code. HISM)RY: 1. Amendment filed 1-1885; effective upon filing pursuant to Government Code Sec- tion 113462(d) (Register 85, No. 6). 66310. vuianees. (a) The Deymay grant a variance from the provisions of this chap ( ter ifa hazar ous waste is: (1) Insiyuf&mr as a potential hazard to human health and safety, livestock, or wildlife use of its small quantity, low concentration or physical or chemi- cal characteristics; or (2) Handled, stored or dispased of pursuant to regulations of another gov- ernmental agency in a manner which is consistent with the hazardous waste management provisions of this chapter and which will not result in a hazard to human health and safety, livestock or wildlife. (b) An application to the Depptment for a variance from a rovision of this (. chapter pursuant to Section 66310(a shall include all of the Pollowing: (1) The name of the producer of 3, e waste and the address where the waste is located. . .. (2) A description of the waste, including its quantity, physical state, composi- tion, source and production rate. (3) A specification of the variance requested. (4) An assessment of the hazardous characteristics of the waste pursuant to the criteria of Article 11. (5) A statement on how the waste is to be managed. (c) The Department may grant a variance requested pursuant to subsection (a) (1) or (a) (2), subject to such conditions or limitations that the Department deems necessary, if the Department hds that the waste meets the provisions of Section 66310(a) (1) or (a) (2). oms ENVIRONMENTAL HEUTH TITLE22 (p. 1800.84) (R-1- a NO. &I-1246) (e) Has an acute dermal LDmless than or qual to 43 milligrams per kilo- c gram; or (3) Has an acute inhalation Lc, less than or equal to 100 parts per million .. as a gas or vapor; or .. * (4) Contains any of the substances listed in Section 66696(a) (5) at a single .. or combined concentration ual to or exceeding 0.1 percent by weight; or ( 5) Has been shown thou3 experi "e or testing to pose an extreme haz- ard to the public health because of its carcinogenicity, high acute or chronic toxicity, bioaccumulative properties, or persistence in the environment; or (6) Is water-reactive. (b) A waste containing one or more materials which are extremely toxic awrato any criterion of paragraphs (a) (1) or (a) (2) of this section may be c ed by the Department as not extremely hazardous if neither the calculated acute oral toxicity nor the calculated acute dermal toxicity of the waste using the equation in Section 66696(c) is numerically equal to or less than the toxicity limits prescribed in paragraphs (a) (1) or (a) (2) of this section and (, the waste is not extremely hazardous by any other criterion of this section. NOTE: Authority cited: Sections 908,25141 and 25150, Health and Safety Code. Refer- ence: Section e5141, Health and Safety Code. HIsroRY: 1. Editorial correction filed 10-584; designated effective 10-27-84 (Register 84, No. 41). 66723. Total Threshold Limit Concentration Values of Persistent and Bioao cumulative Toric Substances in Extremely Hazardous Wastes. (a) Any waste containing a substance listed in subsection (b) of this section at a concentration equal to or exceeding its listed total threshold limit concen- ( tration is an extremely hazardous waste. (b) List of Persistent and Bioaccumulative Toxic Substances and Their Total Threshold Limit Concentration (nzC)Values. 'ITLC (Wet-Weight substance mg/kg) Aldrin ...... 140 Arsenic and/or arsenic compounds...... so,000 (as M Beryllium and/or beryllium compounds...... 7300 (as Be) Cadmium and/or cadmium compounds...... l0,Ooo (as cd) or...... 250 2,4Dichloraphenoxyamtic acid ...... 10,Ooo Dieldrin ...... 800 Dioxin (23,7,&KDD) ...... 1 Endrin ...... 20 Heptachlor ...... 470 Kepone ...... %I00 bad compounds, organic ...... 1,300 (dry weight basis; as Pb) Lindane ...... 400 Mercury andlor mercury compounds ...... %m Hg) Mirex ...... 2,100 Polychlorinated biphenyls (PCBs) ...... 5,000 Selenium andlor selenium compoundso ...... 10,000 (as se) Thallium and/or thallium compoundso ...... 70,000 (as Tl) Toxaphene ...... 500 2,4,!5-TncNorophenoxypropionic acid ...... 1 In the case of elemental metals, applies only if they are in a friable, powdered or finely divided state. State of California CALIFORNIA ADMINISTRATIVE CODE TITLE 23. WATERS Reclamation Board Department of Water Resources State Water Rights Board State Water Quality Control Board 2777E TITLE 23 !STATE WATER RESOURCES CONTROL BOARD 0 2523 (Rogistw M No. 48-12W) (p. 78.20.19) \I 2521. HazardousWaste. (a) Hazardous waste is any waste which, under Section 66300 of Title 22 of this code, is required to be managed according to Chapter 30 of Division 4 of Title 22 of this code. (b) Hazardous wastes shall be discharged only at Class I waste management units which comply with the ap licable provisions of this subchapter unless ‘) wastes ualify for a variance un aer Section 66310 of Title 22 of this code. (c) Jastes which have been desi ated as restricted wastes by DHS pursu- ant to Section 66900, of Title 22 of %s code shall not be discharged to waste management units after the restriction dates established by Section 66905 of Title 22 unless: (1) such discharge is for retrievable storage, and (2) DHS has determined that processes to treat or recycle substantially all of the waste are not available, or (3) DHS has granted a variance from restrictions against land disposal of the waste under Section 66930 of Title 22 of this code. NOTE Authority cited: Section 1058, Water Code. Reference: Sections 13050 and 13172, Water Code. 2522. Designated Waste. (a) Designated waste is: (1) nonhazardous waste which consists of or contains pollutants which, un- der ambient environmental conditions at the waste management unit, could be released at concentrations in excess of applicable water quality objectives, or which could cause degradation of waters of the state. (2) hazardous waste which has been granted a variance from hazardous waste management requirements pursuant to Section 66310 of Title 22 of this 1’ code. (b) Wastes in this category shall be discharged only at Class I waste mana e- ment units or at Class I1 waste management units which com ly with ta e applicable provisions of this subchapter and have been approve for contain- ment of the particular kind of waste to be discharged. DecomposableB wastes in this category may be discharged to Class I or I1 land treatment waste manage- ment units. NOTE:Authority cited: Section 1058, Water Code. Reference: Section 13172, Water Code. 2523. Nonhazardous Solid Waste. (a) Nonhazardous solid waste means all putrescible and nonputrescible solid, semi-solid, and li uid wastes, including garbage, trash, refuse, paper, rubbish, ashes, industri9 wastes, demolition and construction wastes, aban- doned vehicles and parts thereof, discarded home and industrial ap liances, manure, vegetable or animal solid and semi-solid wastes and other iscarded solid or semi-solid waste; provided that such wastes do not contain wastesa which must be managed as hazardous wastes, or wastes which contain soluble pollu- tants in concentrations which exceed applicable water quality objectives, or could caw degradation of waters of the state (ie., designated waste). ) (b) Except as provided in Subsection 2520(d of this article, nonhazardous solid waste may be discharged at any classified Iandfill which is authorized to accept such waste, provided that: 0 2524 STATE WATER RESOURCES CONTROL BOARD TITLE 23 (p. 78.20.20) (Registar 84, No. -12d.04) (1) the discharger shall demonstrate that codisposal of nonhazardous solid waste with other waste shall not create conditions which could impair the integrity of containment features and shall not render designated waste hazard- ous (e.g., by mobilizing hazardous constituents) ; (2) a periodic load-checking program approved by DHS and the regional board shall be implemented to ensure that hazardous materials are not dis- charged at Class I11 landfills. (c) Dewatered sewage or water treatment sludge may be discharged at a Class I11 landfill under the following conditions, unless DHS determines that the waste must be managed as hazardous waste: (1) The landfill is equipped with a leachate collection and removal system; (2) The sludge contains at least 20 percent solids if rimary sludge, or at least 15 rcent solids if secondary sludge, mixtures oP primary and secondary slu 8"ges, or water treatment slud e; and (3) A minimum solids-to-liqui c! ratio of 5:l by weight shall be maintained to ensure that the codisposal will not exceed the initial moisture-holding ca acity of the nonhazardous solid waste. The actual ratio required by the regionalgoard shall be based on site-specific conditions. (d) Incinerator ash may be discharged at a Class I11 landfill unless DHS determines that the waste must be managed as hazardous waste. NOTE: Authority cited: Section 1058, Water Code. Reference: Section 13172, Water Code. 2524. Inertwaste. (a) Inert waste does not contain hazardous waste or soluble pollutants at concentrations in excess of applicable water quality objectives, and does not contain significant uantities of decomposable waste. \ (b) Inert wastes 3o not need to be discharged at classified waste managment units. (c) Regional boards may prescribe individual or general waste discharge requirements for discharges of inert wastes. NOTE: Authority cited: Section 1058, Water Code. Reference: Section 13172, Water Code. Article 3. Waste Management Unit Classification and Siting 2530. Classification and Siting Criteria. (a) Waste management units shall be classified according to their ability to contain wastes. Containment shall be determined by geology, hydrology, topog- raphy, climatology, and other factors relating to the ability of the waste manage- ment unit to protect water quality. A waste mana ement facility may consist of several waste management units each with a dif Berent classification. Classifi- cation of waste management units shall be based on the criteria contained in this article, on field inspections by regional board and State Board staffs, and rtinent information. Information used to classify waste management Onunits Otherape sh be submitted according to the provisions of Article 9 of this subchap- ter. Classified waste management units shall comply with appropriate waste discharge requirements. (b) Existing waste management units shall be reclassified according to appli- cable criteria in this article, provided that such units: (1) comply with sitin criteria for each category of existing units in Sections 2531,2532, and 2533 oftE is article, and summarized in Table 3.1 of this article, and (2) are operating in compliance with Subsection 2510(d) of this subchapter. J