Ariz. Admin. Code § tit. 18, ch. 2, APPENDICES, app 8
A8.1. Calculating Input Sulfur
Total sulfur input is the sum of the product of the weight of each sulfur bearing material introduced into the smelting process as calculated in A8.1.1. multiplied by the fraction of sulfur contained in that material as calculated in A8.1.2. plus the amount of sulfur contained in fuel utilized in the smelting process as calculated in A8.1.3.
A8.1.1. Material Weight
The owner or operator of a copper smelter shall weigh all sulfur-bearing materials, other than fuels, introduced into the smelting process. The weighing shall be subject to the following conditions:
A8.1.1.1. Weight shall be determined on a belt scale, rail or truck scales, or other weighing device.
A8.1.1.2. Weight shall be determined within an accuracy of ± 5%.
A8.1.1.3. All devices or scales used for weighing shall be calibrated to manufacturer's specifications at least once a month.
A8.1.1.4. Sulfur-bearing materials subject to being weighed include concentrate, cement copper, reverts that are discarded and not part of the internal circulating load and precipitates. Materials such as limestone and silica flux that are mixed with a charge of sulfur bearing materials shall be weighed and reported by the owner or operator.
A8.1.2. Sulfur Content
The owner or operator shall calculate the sulfur content of all sulfur-bearing materials introduced into the smelting process using the following steps or an alternative method approved according to A8.4.1.
A8.1.2.1. Sampling
The procedures followed by the owner or operator in sampling are dependent upon the input vehicles for the sulfur-bearing material.
A8.1.2.1.1. Beltfeed
The smelter owner or operator shall collect a five-pound sample each hour. The owner or operator shall combine hourly samples for a total daily sample.
A8.1.2.1.2. Railcar
The smelter owner or operator shall collect a 24-pound sample from each car by the auger method at a minimum of four locations. The owner or operator shall combine each car sample with all other car samples for a total lot sample.
A8.1.2.1.3. Truck
The owner or operator shall collect a 12-pound sample from each truck load. The owner or operator shall take samples at two locations during unloading. If more than one truck delivers a single lot, the samples from each truck shall be combined for a total lot sample.
A8.1.2.2. Sample Preparation
The owner or operator shall prepare each total sample for analysis in the following manner:
A8.1.2.2.1. The sample shall be crushed to minus 1/4 inch particles.
A8.1.2.2.2. 2000 gm of the sample shall be split out using a Jones Riffle Splitter or similar device.
A8.1.2.2.3. The 2000 gm sample shall be pulverized to minus 150 mesh.
A8.1.2.2.4. The pulverized mass shall be mixed using a rolling cloth.
A8.1.2.2.5. 500 gm shall be split out for sample analysis.
A8.1.2.3. Sample Analysis
A8.1.2.3.1. The owner or operator shall analyze the sample to determine sulfur content using the Barium Sulfate (BaSO4 ) Gravimetric Method according to A8.4.3. The analysis shall be accurate to within ± 1%.
A8.1.2.3.2. For purposes of comparison, the owner or operator shall analyze the sample for copper content using the Potassium Iodide (KI) Titration Method according to A8.4.3. The analysis shall be accurate to within ± 1%.
A8.1.3. Fuel Sulfur Content
The owner or operator shall calculate sulfur in fuels by multiplying the amount of fuel that enters the process by the fraction of sulfur in the fuel, as reported to the smelter operator by the fuel's supplier. The sulfur content determination shall be accurate to within ± 5%.
A8.2. Calculating Removed Sulfur
Total removed sulfur is the sum of the removed sulfur in each of the following products as determined by each process set forth below, or by other processes approved according to A8.4.1.
A8.2.1. Furnace and Convertor Slags
A8.2.1.1. The owner or operator shall determine the weight of each slag using a scale with an accuracy within ± 5%.
A8.2.1.2. The owner or operator shall collect a five-pound sample from each slag pot during tapping operations.
A8.2.1.3. The owner or operator shall prepare the sample and determine the amount of sulfur and copper using the procedures specified in A8.1.2.2. and A8.1.2.3.
A8.2.2. Dust Collection Equipment Dusts
A8.2.2.1. After the owner or operator collects the dust and places it in a rail car or truck they shall weigh it using a scale with an accuracy within ± 5%.
A8.2.2.2. The owner or operator shall sample the dust and prepare and analyze a sample for sulfur and copper using the procedures specified in A8.1.2.1., A8.1.2.2., and A8.1.2.3.
A8.2.3. Strong Acids
A8.2.3.1. The owner or operator shall take an inventory of strong acids daily by means of a manometer or sight glass, and increase the inventory by the amounts of acid shipped or otherwise transferred during that day.
A8.2.3.2. The owner or operator shall ensure the daily inventory will be accurate to within ± 5%.
A8.2.3.3. The owner or operator shall take a sample of each batch of the inventoried acid and analyze the sample for sulfur, according to the procedures in A8.1.2.3.
A8.2.4. Weak Acids
A8.2.4.1. The owner or operator shall determine the amount of weak acid discharged from an acid plant and scrubber systems by a time volumetric method of measurement in gallons per minute and to an accuracy of within ±20%.
A8.2.4.2. The owner or operator shall analyze a 500 ml sample of the weak acid daily for sulfur content according to the procedures in A8.1.2.3.
A8.2.5. Sulfur in Copper Production
A8.2.5.1. The owner or operator shall determine the weight of copper produced by weight of copper cast to an accuracy of within ± 5%.
A8.2.5.2. The owner or operator shall record the weight and number of castings.
A8.2.5.3. The owner or operator shall obtain a sample of the copper, either by the grab sample method while casting, or by the use of at least three drill holes on a representative casting from each charge.
A8.2.5.4. The owner or operator shall obtain at least one sample from each charge.
A8.2.5.5. The owner or operator shall analyze each sample for sulfur content using the Barium Sulfate (BaSO4) Gravimetric Method according to A8.4.3. The analysis shall be accurate to within ± 50%.
A8.2.6. Materials in Process
A8.2.6.1. The owner or operator shall determine the total tonnage of materials in process by physical inventory on the first or last day of each month.
A8.2.6.2. The owner or operator shall calculate a monthly change in in-process inventory for each material in process by taking the difference between the inventory from each material in process on the first or last day of the preceding month and multiplying that difference by the monthly composite sulfur assay for that material.
A8.2.6.3. The change in monthly in-process inventory shall be accurate to within ± 50%.
A8.3. Sulfur Dioxide Emissions Monitoring
A8.3.1. The sulfur dioxide emissions monitoring and recording system required under R18-2-715.01(K) through R18-2-715.01(N) shall meet the following specifications:
A8.3.1.1. The monitoring system shall be capable of continuously monitoring sulfur dioxide emissions with an accuracy of within ±20% and a confidence level of 95%.
A8.3.1.2. The owner or operator shall operate and calibrate the sulfur dioxide emission monitoring and recording equipment according to manufacturer's specifications for the equipment except that calibration shall be done at least once every 24 hours.
A8.3.2. The sulfur removal equipment bypass monitoring required under R18-2-715.01(Q) shall consist of a detector and recorder system capable of producing a permanent record of all periods that the bypass is in operation.
A8.4. General Provisions
A8.4.1. For purposes of this Appendix, an approved alternative method, process, or procedure, must be approved in writing by the Director and the U.S. Environmental Protection Agency.
A8.4.2. The processes and procedures specified in this Appendix shall be available for inspection, review and verification by the Department at all reasonable times.
A8.4.3. The barium sulfate gravimetric test method and potassium iodide titration test method provided in Standard Methods of Chemical Analysis, Volume One, The Elements, Sixth Edition, N. Howell Furman (ed.), D. Van Nostrand Company, Inc., Princeton, New Jersey, 1962, pages 410-411, 1006-1011, and 1342-1343 (and no future editions or amendments) is incorporated by reference and available at the Department.
Ariz. Admin. Code tit. 18, ch. 2, APPENDICES, app 8