Final
Treatability Study Technical Memorandum
Formosa Mine Superfund Site
Douglas County, Oregon
Prepared for: U.S. Environmental Protection Agency
Region 10 1200 Sixth Avenue, Suite 900 Seattle, Washington 98101
Prepared by: CDM Federal Programs 1218 Third Avenue, Suite 1100 Seattle, Washington 98101
Parametrix 411 108th Avenue NE, Suite 100 Bellevue, Washington 98004 R‐10 AES (SMALL BUSINESS) CONTRACT NO. 68‐S7‐03‐04 June 12, 2014
Task Order No. 047B
Final
Treatability Study Technical Memorandum Formosa Mine Superfund Site Douglas County, Oregon
R‐10 AES (SMALL BUSINESS) CONTRACT NO. 68‐S7‐03‐04 Task Order No. 047B
06/12/14 Prepared by: Date Stephen Dent, Ph.D. CDM Smith Project Scientist1
06/12/14 Reviewed by: Date Roger Olsen, Ph.D. CDM Smith Technical Reviewer
06/12/14 Reviewed by: Date David J. Reisman CDM Smith Technical Consultant
06/12/14 Approved by: Date Michael C. Allen, P.E. CDM Smith Project Manager
Distribution List (via email)
Chris Cora Remedial Project Manager EPA Region 10 Seattle, WA
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Section 1 Introduction ...... 1‐1 1.1 Site Description and Background ...... 1‐1 1.2 Purpose of Treatability Study ...... 1‐2 1.3 Treatment Technology Description ...... 1‐2 1.3.1 Biological and Chemical Processes for MIW Treatment in BCRs ...... 1‐2 1.3.2 Factors Impacting BCR Performance ...... 1‐3 1.3.3 ORD Bench‐Scale Studies ...... 1‐3 1.4 Pilot‐Scale Treatability Study Objectives ...... 1‐4 1. 5 Pilot‐Scale Treatability Study Approach ...... 1‐4 1.5.1 Formosa 1 Adit Chemistry ...... 1‐5 1.5.2 Pre‐Treatment Methods ...... 1‐5 1.5.3 BCRs ...... 1‐6 1.5.4 Post‐Treatment ...... 1‐6 1.5.5 Treatability Study System Layout and Design Flow Rate ...... 1‐6 1.5.5.1 System Layout ...... 1‐6 1.5.5.2 System Flow Rate ...... 1‐7 Section 2 Pilot Study Methods and Sampling ...... 2‐1 2.1 Collection and Routing of MIW ...... 2‐1 2.2 Pre‐Treatment System Installation ...... 2‐2 2.2.1 SAPS Pre‐Treatment System ...... 2‐2 2.2.2 ChitoRem® Pre‐Treatment System ...... 2‐3 2.3 Installation of Biochemical Reactors ...... 2‐3 2.4 System Startup, Operation and Maintenance, and Shutdown ...... 2‐4 2.4.1 System Startup ...... 2‐4 2.4.2 Operation and Maintenance ...... 2‐5 2.4.3 System Shutdown ...... 2‐9 2.5 Pilot Study Sampling ...... 2‐9 2.5.1 Sampling Activities ...... 2‐9 2.6 Deviation from the Pilot Study Work Plan (PSWP) and Quality Assurance Project Plan (QAPP) ...... 2‐10 2.6.1 Deviation from PSWP and QAPP ...... 2‐10 Section 3 Evaluation Criteria, Results, and Discussion ...... 3‐1 3.1 Pilot Study Evaluation Criteria ...... 3‐1 3.1.1 MRE ...... 3‐1 3.1.2 Water Quality ...... 3‐1 3.1.3 Pre‐Treatment and BCR System Operation and Maintenance Considerations ...... 3‐2 3.2 Results and Discussion ...... 3‐2 3.2.1 MIW Influent ...... 3‐2 3.2.2 BCR Barrels 1 and 2 ...... 3‐3 3.2.3 SAPS Pretreatment with BCR 3 and 4...... 3‐9 3.2.4 ChitoRem® Pretreatment with BCR Barrels 5 and 6 ...... 3‐15 3.2.5 ChitoRem® Permeability ...... 3‐20 3.3 Data Validation and Usability ...... 3‐21
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Section 4 Conclusions and Recommendations ...... 4‐1 4.1 Pilot‐Scale Treatability Study Conclusions ...... 4‐1 4.2 Considerations for Future Design ...... 4‐4 Section 5 References ...... 5‐1
List of Tables
Table 1‐1 Formosa 1 Adit Water Quality Data Table 1‐2 Composition of Pre‐Treatment Materials Table 1‐3 BCR and Pre‐Treatment Substrate Percentages and Volumes Table 2‐1 Headspace Concentrations after One Month Stagnation Period Table 2‐2 Formosa Treatability Study Sampling and Analysis Summary Table 2‐3 Formosa Treatability Study Field Activity Timeline Table 3‐1 Surface Water Quality Comparison Values Table 3‐2 Analytical Results Table 3‐3 Sulfate Reduction Table 3‐4 Dissolved Metals Removal Efficiency Table 3‐5 Sulfate Reduction
List of Figures
Figure 1‐1 Pilot‐Scale Treatability Study Water Treatment System Figure 1‐2 Pilot‐Scale Treatability Study Process Flow Diagram (Record Drawing) Figure 2‐1 HDPE Pipe Installation at Adit Portal Figure 2‐2 Feed Tank Installation Figure 2‐3 Pre‐Treatment and BCR Barrel Drainage Manifold Figure 2‐4 Configuration of Treatability System Figure 2‐5 Configuration Example of Influent Diversion using a Timer Valve between BCR 1 and BCR 2 Figure 3‐1 pH Measurements Figure 3‐2 Conductivity Measurements Figure 3‐3 Dissolved Oxygen Measurements Figure 3‐4 Oxidation‐Reduction Potential Measurements Figure 3‐5 Temperature Measurements Figure 3‐6 Daily Temperature Measurements Figure 3‐7 Dissolved Aluminum Concentrations Figure 3‐8 Dissolved Arsenic Concentrations Figure 3‐9 Dissolved Cadmium Concentrations Figure 3‐10 Dissolved Calcium Concentrations Figure 3‐11 Dissolved Chromium Concentrations Figure 3‐12 Dissolved Copper Concentrations Figure 3‐13 Dissolved Iron Concentrations Figure 3‐14 Dissolved Manganese Concentrations Figure 3‐15 Dissolved Nickel Concentrations Figure 3‐16 Dissolved Zinc Concentrations
Figure 3‐17 Total Alkalinity (as CaCO3) Concentrations Figure 3‐18 Sulfate (as SO4) Concentrations
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List of Figures (continued)
Figure 3‐19 Sulfide Concentrations Figure 3‐20 Acetic Acid Concentrations Figure 3‐21 Trace Mercury (Round 4)
List of Appendices
Appendix A ChitoRem® Sediment Core Permeability Testing Appendix B Formosa Mine Treatability Study Data Evaluation
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Acronyms °C degrees Celsius °F degrees Fahrenheit AES architectural and engineering services Al aluminum amp/hr amperes per hour amsl above mean sea level APC aerobic polishing cell As arsenic ASTM American Society for Testing and Materials Ba barium BCR biochemical reactor BLM U.S. Department of the Interior Bureau of Land Management BOD biological oxygen demand Ca calcium CaCO3 calcium carbonate Cd cadmium CDM Smith CDM Federal Programs Corporation CERCLA Comprehensive Environmental Response, Compensation, and Liability Act CLP Contract Laboratory Program cm/sec centimeters per second Co cobalt COD chemical oxygen demand Cr chromium Cu copper CVAA cold vapor atomic absorption DO dissolved oxygen DOC dissolved organic carbon EPA United States Environmental Protection Agency ERRG Engineering/Remediation Resources Group Fe iron FID flame ionization detector FS feasibility study ft amsl feet above mean sea level GANDA Garcia and Associates g/mL grams per milliliter gal/day gallons per day gpm gallons per minute HDPE high‐density polyethylene Hg mercury ITSI Innovative Technical Solutions, Inc., a Gilbane Company IV intravenous K potassium kg/L kilograms per liter L liter L/hr liters per hour L/min liters per minute MDL maximum detection limit MeHg methylmercury MEL Manchester Environmental Laboratory Mg magnesium
vii Acronyms
mg/L milligrams per liter mg/m3 milligrams per cubic meter mil milli‐inch MIW mining influenced water mL milliliter ml/day milliliters per day ml/min milliliters per minute Mn manganese MRE metal removal efficiency MRL method reporting limit mS/cm milliSiemens per centimeter MS/MSD matrix spike/matrix spike duplicate mV millivolts Na sodium NaOH sodium hydroxide NFG National Functional Guidelines ng/L nanograms per liter Ni nickel O&M operation and maintenance ODEQ Oregon Department of Environmental Quality ORD Office of Research and Development ORP oxidation‐reduction potential OU operable unit PARCCS precision, accuracy, representativeness, comparability, completeness, and sensitivity Pb lead PID photoionization detector PMDA primary mine disturbance area psi pounds per square inch PSWP pilot study work plan PVC polyvinyl chloride QA quality assurance QAPP quality assurance project plan QC quality control RI remedial investigation SAP sampling and analysis plan SAPS successive alkalinity producing system Site Formosa Mine Superfund Site in Douglas County, Oregon SPAF sample plan alteration form SPLP synthetic precipitation leaching procedure SRB sulfate‐reducing bacteria su standard unit TAL target analyte list TDS total dissolved solids THg total mercury TO task order TTWP treatability testing work plan µg/L micrograms per liter µS/cm microSiemens per centimeter USFS United States Forest Service VFA volatile fatty acids WRP waste rock pile Zn zinc
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Section 1 Introduction
CDM Federal Programs Corporation (CDM Smith) was tasked by the United States Environmental Protection Agency (EPA) Region 10 to conduct a pilot‐scale treatability study at the Formosa Mine Superfund Site (Site) in Douglas County, Oregon. This effort is being conducted within Task Order 047 for Architectural and Engineering Services (AES10) Contract Number 68‐S7‐03‐04. The treatability study is part of the remedial investigation/feasibility study (RI/FS) for Operable Unit (OU) 2.
This technical memorandum documents the purpose, objectives, methods, analyses, results, and recommendations of the treatability study specifically at the Formosa 1 Adit discharge. This treatability study was conducted in accordance with the approved Treatability Study Work Plan for Operable Unit 2 Remedial Investigation/Feasibility Study at Formosa Mine Superfund Site, dated June 2013. This pilot‐scale treatability study was designed in consultation with the EPA document Guidance for Conducting Treatability Studies under CERCLA, EPA/540/G‐92/071a, October 1992, Final (EPA 1992). Specialized EPA treatability guidance for mining influenced water (MIW) is not available. 1.1 Site Description and Background The Site is an abandoned mine located in southwest Oregon in Douglas County, approximately 25 miles south of Roseburg, Oregon, and 7 miles south of Riddle, Oregon. Specifically, the Site is located within Sections 23, 26, and 27, Township 31 South, Range 6 West Willamette Meridian. Locally, it is situated in the Coast Range Klamath Mountains at elevations between 3,200 and 3,700 feet above mean sea level (amsl) near Silver Butte Peak (3,973 feet amsl).The Site is divided into two OUs:
. OU1 includes all surface and subsurface mine materials and contaminated soils deposited outside of the underground mine workings.
. OU2 includes all remaining media and site contamination areas, including surface water, stream sediment, groundwater, underground workings, and adit water drainage.
The primary mine disturbance area (PMDA) for OU1 is the portion of the Site that has been impacted by surface deposition of mine materials as a result of mining‐related activities. The PMDA encompasses approximately 24.4 acres.
Surface terrain is characterized by steep mountains, narrow ridges, and deep canyons. The upland area surrounding the PMDA of the Site is heavily forested, consisting predominantly of Douglas fir. The Site is situated near the top of a mountain ridge (Silver Butte ridge) that divides several sub‐ watersheds and drainages. Russell Creek drainage lies to the north of the Site, Upper West Fork Canyon Creek drainage lies to the east, South Fork Middle Creek drainage lies to the south, and Upper Middle Creek drainage lies to the west.
The Formosa 1 Adit, the focus of this treatability study, is located on the northern end of the Site above the Formosa 1 Adit waste rock dump and within the Upper Middle Creek watershed. Upper Middle Creek is severely affected by mining‐influenced water (MIW) and associated releases of contaminants of potential concern from mine materials present on the surface and discharge from the Formosa 1 Adit.
1‐1 Section 1 Introduction
Additional background on the site is provided in the RI report for OU1 (CDM Smith 2012). 1.2 Purpose of Treatability Study The treatability study was conducted to evaluate ex‐situ passive treatment options for the Formosa 1 Adit discharge as part of the OU2 RI/FS. This testing is being performed to evaluate effectiveness of passive biological treatment of MIW. The purpose of the treatability study is to evaluate the effectiveness of a particular process option and/or substrate with regard to reduction of metal and sulfate concentrations and neutralization of acidic water. In addition, the study will provide engineering data for practical considerations of a potential full‐scale implementation. This final draft of the technical memorandum will be used to support technology screening conducted in the Phase 1 Feasibility Study Treatment Technology Screening Memorandum through the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) remedy selection process. These evaluations will be conducted as part of the OU2 FS. 1.3 Treatment Technology Description BCRs are engineered systems that use an organic substrate (electron donor) to drive microbial and chemical reactions to reduce concentrations of metals, acidity, and sulfate in MIW (CDM Smith, 2013a). For this Site, a laboratory bench scale treatability study was conducted by EPA’s Office of Research and Development (ORD) in Cincinnati, Ohio. In addition, Formosa 1 Adit treatability bench‐ scale tests were initiated by the State of Oregon Department of Environmental Quality (ODEQ) and reported in 2000 (Hart Crowser2000). Available information from these previous studies and experience at other sites were used to develop the approach of this pilot study. 1.3.1 Biological and Chemical Processes for MIW Treatment in BCRs A BCR involves a biologically mediated process in which an organic substrate is provided as an electron donor for sulfate‐reducing bacteria (SRB) to reduce sulfate present in the MIW to various aqueous sulfide species. Subsequently, the metals present in MIW react with the sulfide species to form metal sulfide precipitates such as iron, copper, nickel, and zinc sulfides. Formation of metal sulfide precipitates is the dominant mechanism by which metals are removed in the BCR over the long term. The biological mediated sulfate reduction reaction can be simplified as follows:
‐2 ‐ ‐ + SO4 + 2 CH2O HS + 2 HCO3 + H
‐2 ‐ ‐ Sulfate reduction produces both reduced sulfide (S and HS ) and alkalinity via carbonate (HCO3 ), resulting in net increase in pH on the MIW during the reaction. The formation of metals sulfides proceeds generally as follows (where Me = divalent metal species):
S2‐ + Me2+ MeS(s) and HS‐ + Me2+ MeS(s) + H+
CH2O in the sulfate reduction reaction is a generic representation of an organic substrate. The actual form of organic compound utilized by SRB to reduce sulfate can be complex and can vary for each substrate or combination of substrates. The availability of a readily usable carbon source by SRB is the limiting factor for the overall sulfide generation and subsequent metal removal rate. Solid substrates must proceed through an anaerobic fermentation process to produce a soluble form of carbon, and a consortium of bacteria is involved in this process. Common cellulosic‐based solid substrates utilized in BCRs include wood chips, sawdust, hay, and compost. Anaerobic fermentation of cellulosic materials
1‐2 Section 1 Introduction
converts sugars into volatile fatty acids (VFAs) such as lactic acid that is used by the SRB to reduce sulfate.
BCR treatment can be implemented at full‐scale utilizing a gravity‐fed cell filled with substrate material that treats the MIW. Substrate within the BCR cell is most commonly a solid substrate mix of woody materials (e.g., wood chips, shredded wood, sawdust, hay, and straw), compost, manure, limestone gravel, and/or inert gravel. A number of other solid materials may be used in the BCR such as crab and oyster shells, rice hulls, walnut shells, other food waste materials, and inert sand and gravel. Materials are selected not only for their organic contents but also with considerations on the surface areas they provide for the microbial biofilm to form and to attach and the porosity for water to flow through.
As part of a passive treatment system, a BCR cell is commonly followed by aeration processes, which may include cascades and an aerobic polishing cell (APC). Aeration provides oxidation to the BCR effluent to decrease sulfides, increase dissolved oxygen (DO), transform ammonia to nitrate, and reduce biological oxygen demand (BOD) formed from organic substrates prior to discharge to receiving water. In addition, the aeration processes provide settling capacity for residual suspended solids and metals polishing treatment similar to a surface wetland. Without the aeration processes, the effluent from BCR treatment might be toxic to some microorganisms/species in a receiving water body. 1.3.2 Factors Impacting BCR Performance Several factors can impact the effectiveness of a BCR, including:
. Fluctuation of MIW geochemistry and flow: decrease of pH, increase of oxygen level and metal concentrations, and increase of flow rate in MIW
. Availability of readily available electron donor: the type of organic substrate
. Porosity of the BCR media and retention time of the BCR system: adequate contact time for the biological and chemical treatment processes to occur
. Suitable source of sulfate‐reducing bacteria 1.3.3 ORD Bench‐Scale Studies A laboratory bench‐scale treatability study was initiated by the ORD laboratory in Cincinnati, Ohio, in summer 2012 and continued through the year and into spring 2013. Preliminary results were provided to CDM Smith in February 2013 to aid in the design of this pilot‐scale treatability study.
The bench‐scale treatability study included proof‐of‐principle batch tests first, followed by flow‐ through column studies with different substrates. Water used for the study (over 200 gallons) was collected from Formosa 1 Adit discharge in anaerobic tanks (under nitrogen gas all the time during collection and storage) and shipped to the ORD laboratory. Both pre‐treated (i.e., neutralized) and non‐pre‐treated column tests were conducted side by side, with two substrate types tested for each pre‐treated and non‐pre‐treated water batch. The pre‐treatment used sodium hydroxide (NaOH) to raise the pH to 6.7 standard units (su). The two substrate types tested were (1) ChitoRem® SC‐20® (ChitoRem®) and sand mixture and (2) a woody material mixture containing wood chips, hay, and manure. A third set of column tests were conducted using inert media as an abiotic control. (Al‐Abed 2013 personal communication)
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Column tests were started in May 2012 and continued through March 2013. Columns were allowed to adapt to Site water for 12 weeks (no flow through) followed by continuous flow through operation. Flow rates to each column were initiated at 89 milliliters per day (ml/day) for a period of 16 weeks followed by increasing flow rates to 178 ml/day for 16 weeks. Preliminary results showed that metal removal occurred in all four columns with or without pre‐treatment using both ChitoRem® with sand and the woody material mixture. This laboratory study proved that the MIW at Formosa 1 Adit could be treated passively (Al‐Abed 2013 personal communication). 1.4 Pilot‐Scale Treatability Study Objectives The pilot‐scale treatability study was conducted to support the ongoing OU2 RI/FS in technology evaluation for source control, management, and possible treatment of the adit discharge and mine pool water. Conducting the pilot‐scale testing is compatible with the current phase of the CERCLA process for OU2 in 2013. The objectives of this study are:
1. Evaluate the effectiveness of passive treatment technology using BCRs with site‐specific conditions
2. Provide site‐specific data for the design of full‐scale MIW treatment system at the Formosa 1 Adit
3. Provide data for evaluation of technologies and development of alternatives for MIW treatment in the OU2 FS
Based on the results of the bench‐scale treatability studies and knowledge from tests at other mine sites, Site‐specific application data to be collected for the Formosa 1 Adit discharge were identified as follows:
. The necessity and effectiveness of pre‐treatment to condition the water for BCR treatment
. MIW loading rate for each BCR medium to achieve effective metal reduction and pH neutralization
. Metals removal efficiency (MRE) and sulfate reduction rate for assessing reduction of contaminant toxicity, mass, and volume, through treatment using BCRs
. Residuals generation rates (i.e. sludge from precipitation) for operation and maintenance (O&M) consideration
. Replacement rate for spent treatment media (substrate for biochemical reactor or limestone in a pre‐treatment process) for O&M consideration
. Impacts of wet weather on the treatment effectiveness and how the BCRs would respond to such changes 1.5 Pilot‐Scale Treatability Study Approach In order to meet the objectives of the pilot‐scale treatability study, the design of the pilot study approach consisted of evaluation of the influent water quality, selection of pre‐treatment methods, selection of BCR media, design of treatment system flow or retention time, and system layout. The development of the pilot study treatability study approach is detailed in the Draft Treatability Study
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Work Plan (CDM Smith, 2013b). A plan view schematic of the treatability testing area is shown on Figure 1‐1. The process flow diagram is shown as Figure 1‐2. A general overview of the pilot‐scale treatability study approach is provided in the subsections below. 1.5.1 Formosa 1 Adit Chemistry Data collected during the OU1 RI and from sampling events in September 2011, February 2012, and September 2012 are used to establish the basic understanding of water quality of Formosa 1 Adit discharge as shown in Table 1‐1. The Formosa 1 Adit discharge is characterized as calcium‐sulfate type water with low pH (ranging from 2.1 to 3.3 su), high metals, and high sulfate. The discharge changes seasonally where marked increases in metals concentrations and decreases in pH occur during the wet season. This effect is thought to occur because the increased precipitation water percolates into the underground mine area, rinses soluble precipitates into the MIW being discharged, and results in a flushing of readily soluble metals and sulfate.
In an acidic MIW type as Formosa 1 Adit discharge, the high iron and aluminum concentrations under oxidizing conditions can form aluminum and iron oxyhydroxide precipitates. The rate of precipitation varies with changes in DO. An increase in DO generally results in a more positive oxidation‐reduction potential (ORP), which generally result in higher rates of precipitation. These precipitates can potentially plug the BCR piping and substrate layers and possibly cause premature failure of a treatment system. Therefore, the BCR treatment for Formosa 1 Adit discharge might benefit significantly from a pre‐treatment system. Testing pre‐treatment processes is critical to this pilot‐ scale treatability study. In addition, a pre‐treatment system may potentially enhance the efficiency and longevity of BCRs although the longevity impacts will not be evaluated here considering the relatively short period (4 months) of the planned study. 1.5.2 Pre‐Treatment Methods Pre‐treatment is used to condition the MIW such as decrease the DO, increase the pH, and provide an initial metals removal stage to minimize the impact of MIW to SRB in the BCRs. It also provides a buffer for the BCRs during wet weather conditions. Two pre‐treatment systems of the adit MIW were designed: a successive alkalinity producing system (SAPS) and an organic substrate (ChitoRem SC20®, referred to as ChitoRem® for the remainder of this document) process. The SAPS system was designed with limestone, and an organic substrate layer above the limestone (down‐flow system), whereas the ChitoRem® process was designed with a blend of ChitoRem® mixed with sand and pea gravel. ChitoRem(SC20)® is a proprietary material from JRW Bioremediation LLC that contains 30 percent by weight calcium carbonate, 40 percent protein, and 20 percent processed crab shells (chitin). Over time, ChitoRem® disintegrates into tiny particles that foster the dissolution of carbonates associated with crab shell chitin that produce alkalinity (Robinson‐Lora and Brennan 2009). The sand and pea gravel were mixed with ChitoRem® to enhance porosity for water flow. The composition of each pre‐treatment mixture is shown in Table 1‐2.
Both the SAPS and the ChitoRem® are passive pre‐treatments that rely upon gravity flow. For the SAPS, the influent MIW first passes through an organic layer that induces oxygen consumption that will help reduce the MIW oxidation state followed by treatment through a limestone layer to increase the alkalinity to elevate the pH. The lowered oxidation state promotes iron reduction to a ferrous form, which helps to limit armoring. Armoring occurs when metal oxides form insoluble precipitates on the limestone surface, subsequently hindering limestone dissolution and the treatment effectiveness (Sun et al. 2000). For the ChitoRem®, the blend of materials provides a similar reaction component, except that the crab shells (provides calcium carbonate) are mixed within the protein
1‐5 Section 1 Introduction
complex layer. Both pre‐treatment processes provide protection for the BCR from spikes in influent metals concentrations, DO increases, and low pH. In the presence of a reduced water oxidation state, the amount of precipitate and the rate at which these precipitates form would decrease thereby affording benefits to the BCR process. 1.5.3 BCRs The key component of the BCR treatment is the substrate utilized as an electron donor for the SRB. Two types of substrate mixes were selected for the pilot study: a ChitoRem® and sand mixture and an almost industry standard of woody material mixture containing wood chips, sawdust, compost, manure, and limestone gravel. The composition of these mixtures has been selected based on literature research, CDM Smith’s experience with testing at other sites, and consistency with the ORD bench‐scale tests, with slight modifications to the woody substrate and limestone mixture as shown in Table 1‐3. For the ChitoRem® and sand mixture, the same blend used for pre‐treatment was used for the BCR treatment. For the woody material mixture, a combination of wood chips and sawdust provides a long‐term source of carbon (large wood chips) as well as an attachment surface for the microbial community. The small particle source (sawdust) may be more readily degradable due to greater exposed surface area.
Additionally, a suitable source of SRB must be present. Often the bacteria are contained within the organic material to be used as a partial substrate (such as manure). For the ChitoRem® and sand mixture, ChitoRem® contains its own bacteria, and over time the material decomposes into smaller particles, which enhances the dissolution of carbonates that produce alkalinity. For the woody mixture, well‐decomposed compost is readily degraded and can provide an abundance of anaerobic fermenting bacteria for the water treatment. The dairy manure also provides these fermenters, as well as SRB and other microbes that form a microbial consortium to inoculate the system, and immediately available carbon as an electron donor. Lastly, the limestone gravel provides structure to the system to reduce long‐term compaction effects and an alkalinity source for buffering the system. 1.5.4 Post‐Treatment Post‐treatment oxidation processes are standard for the effluent from BCRs. For the Formosa 1 Adit pilot‐scale treatability study, testing of a method to achieve post‐treatment oxidation was not conducted. The design effluent discharge volume represented less than 3 percent of the total adit water diversion flow (CDM Smith, 2013b). Post treatment oxidation was anticipated to be achieved during flow through the existing diversion system. 1.5.5 Treatability Study System Layout and Design Flow Rate The pilot scale treatability study was designed to be a passive treatment system requiring minimal operation and maintenance. Flow from the MIW source, through different treatment systems, to final discharge of treated water were all by gravity.
1.5.5.1 System Layout The MIW for this pilot‐scale treatability study was collected by pipe at the adit portal and routed via flow to a water storage feed tank located adjacent and to the north of the Formosa 1 Adit. The 230‐ gallon feed tank was equipped with an overflow bypass that continuously discharged MIW back to the adit water diversion system. From the feed tank, adit MIW gravity flowed through pre‐treatment processes, followed by treatment in the BCR barrels, and discharge to lower portion of the adit water diversion system. The layout of the pilot‐scale treatment system is shown on Figure 1‐1.
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A total of two pre‐treatment barrels and six BCR barrels are tested to compare the performance of two BCR substrates with two selected pre‐treatment systems and with a non‐pre‐treatment system. The process flow diagram is shown in Figure 1‐2. Feed tank and three head tanks were designed to control the flow rates and equal distribution of MIW to the treatment systems.
1.5.5.2 System Flow Rate The total system flow rate is the key factor to design of the pilot‐scale system. Flow rate can be calculated based on the BCR substrate volume, design hydraulic retention time, and design porosity as follows:
Qd = Vs/tBCR*ηs
Where,
Qd = BCR design flow rate, gallons per minute (gpm)
Vs = BCR volume, gallons tBCR = BCR substrate hydraulic retention time, hours
ηs = BCR substrate effective porosity, percent
Using a targeted hydraulic retention time of 24 hours, a substrate volume of 35 gallons, and a substrate porosity of 0.40, the target flow rate for the pilot‐scale system for each BCR reactor is approximately 0.01 gpm (14 gallons per day [gal/day] or 37 milliliters per minute [ml/min]). Since there are six BCR barrels, the total system design flow rate is 0.06 gpm (84 gal/day). The calculations are provided in the Draft Treatability Study Work Plan (CDM Smith, 2013b).
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Section 2 Pilot Study Methods and Sampling
2.1 Collection and Routing of MIW The pilot‐scale treatability study MIW was collected from the Formosa 1 Adit portal via a 2‐inch diameter high‐density polyethylene (HDPE) pipe. The pipe was inserted into the existing adit portal hole with surface MIW flow (approximately 18 inches by 12 inches at an elevation of 3,320 feet above mean sea level [ft amsl]). To secure the pipe inside the portal hole, the adit portal was excavated so that a 2‐ inch pipe could be lain down with the end below the surface of the pooling water in the existing portal pooling area. A weight was used to anchor the drain pipe, which was set 2 feet into the ground and then buried. The weight was constructed and attached to the influent HDPE pipe. The weight consisted of a polyvinyl chloride (PVC) pipe (i.e., 2‐inch diameter) approximately 2 to 3 feet long, filled with sand and secured with end caps. The PVC pipe was attached to the HDPE influent pipe using stainless steel cables, clamps, and zip ties and inserted into the portal hole. The apparatus stabilized the influent pipe and provided weight to ensure the inlet was submerged into the portal hole. Fill material was then packed over the pipe to reform the collection pool. Another 2‐foot piece of pipe was installed several inches above the drain pipe and overflows to allow excess accumulation to flow out the overflow rather than over the top to prevent dam material from blowing out. The drainage portal configuration is shown in Figure 2‐1.
Water flowed into the pipe passively via gravity and into the feed water tank for the treatability study. The feed water tank was installed along the flat ledge area to the north of the Formosa 1 Adit portal area, approximately 50 feet from the adit portal hole at an elevation of 3,312 ft amsl. The influent water collection pipe was sloped at a minimum grade of 2 percent to ensure positive drainage to the feed tank. To provide stability and maintain grade, the pipe was anchored to trees located along the top of the embankment of the flat ledge area using stainless steel cables and clamps. The pipe run was secured from lateral movement along the embankment using steel T‐posts and tie wire.
Just prior to the feed tank, a 2‐inch PVC globe valve was installed on the influent line to provide a water shutoff to the system for maintenance and for flow control. The outlet of the globe valve was converted to 2‐inch PVC, a 90‐degree PVC elbow, and then secured through a drilled hole in the feed tank lid. The feed tank was a plastic 230‐gallon cylindrical leg tank with a screw top lid and equipped with pre‐drilled effluent holes on both sides of the tank. The feed tank was covered but not sealed airtight. The flat ledge area was leveled with hand tools to provide a proper footing for the tank and a level surface. The feed tank was raised on concrete blocks to provide more head to operate the remainder of the system.
The total design system flow rate was 84 gal/day. The feed tank was 230 gallon with an overflow at the top to provide a constant head to feed the system. If any blockage or other failure occurred at the inlet to the feed tank, it could feed the system for 2.7 days. Therefore, a large pipe size (2‐inch HPDE) was used at the inlet and regular inspection and maintenance of the influent line was conducted to ensure continuous flow. The regular maintenance performed included inspection of influent globe valve and pipe for sediment/sludge buildup and inspection of the pipe inlet at the adit portal.
As shown on Figure 2‐2, one tank outlet was utilized for the influent line to the treatment system, and one tank outlet was used for the overflow line to discharge MIW back to the existing adit water
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diversion system. The overflow was constructed of 2‐inch PVC pipe and consisted of an elbow and a riser pipe equipped with a slip union followed by a second elbow connected to 2‐inch HDPE pipe. The 2‐ inch HDPE pipe then passively drained into a 4‐inch HDPE pipe to eliminate any backpressure on the overflow line. The elevation of the overflow line was approximately 2 inches below the top of the feed tank to prevent overflow from the top of the tank itself.
The tank effluent line providing MIW to the treatment system was constructed with 1‐inch PVC pipe, equipped with a sample port, a PVC globe valve, and a watering timer valve. The sample port allowed for influent sampling and capability to drain the tank if necessary; the globe valve provided shutoff capability and flow control, and the watering timer valve was set to open at approximately 3.5‐hour intervals throughout each day. The watering timer valves ran on standard AAA batteries and were changed out every 2 weeks. After the watering timer valve, MIW flowed into three head tanks feeding the treatment system. The timer was set to open for 15 minutes for each head tank filling interval, a length of time that was determined to provide the minimum required volume of MIW to enter each of the three head tanks to feed the treatment system.
The head tank array was installed adjacent to the 230‐gallon feed tank in the flat bench area. The head tank inlet was set at an elevation lower than the feed tank. The three head tanks were connected in a series, including an overflow line after the last head tank. Head tanks were constructed using 5‐gallon buckets with lids (to limit rain and litter infiltration). The connections between each bucket were installed using 1‐inch PVC pipe, fittings, and silicone sealant, and at a height within the buckets to provide the required batch volume. The last head tank had an effluent at the same elevation as the influent and was combined with the overflow pipe from the feed tank using a 2‐inch HDPE pipe.
Because there were a total of six BCR barrels fed by the three head tanks, the target flow rate for each head tank was twice the BCR flow (0.02 gpm or 0.08 liters per minute [L/min]). Instead of continuously feeding the BCRs, MIW was initially fed in batches at approximately 3‐hour intervals. At 0.08 L/min, the volume for 3 hours was approximately 14 liters. To minimize overflow from the three head tanks, the system was calibrated during the startup so that the feed tank effluent timer valve only opened to provide time to fill the head tanks, approximately 15 minutes.
The effluent of each head tank (at the bucket bottom) was equipped with a bulkhead fitting and timer valves. These valves were programmed to open after the head tanks are full to discharge half of the batch of MIW into each corresponding pre‐treatment barrel or the corresponding BCR. 2.2 Pre‐Treatment System Installation Two pre‐treatment systems were constructed. As shown on Figure 1‐2, SAPS pre‐treatment was connected to Head Tank 3 MIW (flow line 3), and a ChitoRem® and sand mixture pre‐treatment was connected to Head Tank 2 MIW (flow line 2). Flow from Head Tank 1 was directly fed into the BCRs without pre‐treatment. 2.2.1 SAPS Pre‐Treatment System A SAPS system was installed in a plastic 55‐gallon barrel. The barrel was filled with approximately 7.5 gallons of inert gravel at the bottom (approximately 5 inches) and 35 gallons of substrate materials (approximately 20 inches) and had approximately 10 inches of space on the top to provide a free water surface and headspace. The substrate materials consisted of ½‐inch size limestone gravel, overlain by a manure and compost layer. By volume percent, the manure/compost layer consisted of approximately 25 percent of the volume (9 gallons), and the limestone accounted for approximately 75 percent of the
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volume (26 gallons). The manure and compost mixture were split evenly (4.5 gallons for each material). The composition is also shown in Table 1‐2.
A piping gallery installed on top of the substrate materials, consisted of a four‐way cross tee and PVC perforated pipes (an X shape of piping) with 3/32‐inch to ¼‐inch holes drilled in the PVC to distribute flow evenly across the surface of the substrate layer and limit preferential pathway formation/short‐ circuiting. Smaller holes were drilled closer to inlet while larger holes were drilled near the outer edges of the pipe runs. No holes were drilled within the last 2 inches from the barrel wall.
An effluent piping gallery was also installed similar to the influent piping gallery and embedded at the bottom of the barrel in the inert gravel layer. This piping gallery was connected to a bulkhead fitting through the barrel bottom and then connected to a flexible hose (e.g., 1‐inch PVC braided tubing). The hose was routed through an upside down U shape drainage manifold to keep the water level in the barrel at approximately 28 inches from the bottom of the barrel, approximately 3 inches above the substrate layer, to keep the substrate saturated and prevent any air from entering into the system (other than from the MIW influent) throughout the treatability study. Two sampling ports were installed in the inverted U‐shaped manifold. The first was installed approximately 6 inches above the effluent port in the barrel. This port was installed to be able to extract accurate DO and redox readings along with pH, conductivity, and temperature parameters from the effluent prior to exposure to air from the anti‐ siphon vent. This lower port usage was minimized because it induces a large head differential within the barrel that could disturb the substrate. The second sampling port was installed in the upper portion of the inverted U‐shaped manifold. This port was installed to be able to extract effluent samples for analysis at a low head differential. Following the sampling port, the effluent drained into the BCR barrels via a ½‐inch hose (BCR 3 and BCR 4). 2.2.2 ChitoRem® Pre‐Treatment System The ChitoRem® pre‐treatment system was installed in the same design as for the SAPS pre‐treatment described in Section 2.2.1. The variation was the replacement of the SAPS substrate with the ChitoRem® substrate mixture, which was a mixture of approximately 20 percent inert pea gravel, 40 percent standard construction sand, and 40 percent ChitoRem® by volume (Table 1‐2). 2.3 Installation of Biochemical Reactors As shown on Figure 1‐1, BCR treatment was conducted in the flat bench area adjacent to the existing adit water collection pond. This treatment area is located down‐gradient from the pre‐treatment barrel location. The difference in elevations of these two areas provided adequate head to feed the BCRs by gravity flow. A total of six 55‐gallon BCR barrels were installed with two types of substrate mixes: (1) a ChitoRem® and sand mixture and (2) a woody material mixture containing wood chips, sawdust, compost, manure, and limestone gravel (Table 1‐3) in alternating barrels. As shown in Figure 1‐2, the effluent flow from Head Tank 1 without pre‐treatment (line 1) was fed to BCR 1 and BCR 2, the effluent from the ChitoRem® pre‐treatment system (line 2) was fed to BCR 5 and BCR 6, and the effluent from SAPS ChitoRem® pre‐treatment system (line 3) was fed to BCR 4 and BCR 5. BCR 1, BCR 3, and BCR 5 were filled with the woody material mixture; and BCR 2, BCR 4, and BCR 6 were filled with ChitoRem® and sand mixture.
The BCR barrels were installed in a similar manner as the SAPS barrel described above. These similarities include the influent and effluent MIW distribution piping gallery, volume of substrate (35 gallons), 4‐inch inert gravel drain layer on the bottom of each (7.5 gallons), effluent piping collection gallery, effluent bulkhead fitting, a U‐shaped effluent manifold to provide the operational tank water
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level, and effluent sampling ports. Effluent discharge from all six BCR barrels via ½‐inch braided PVC tubing were combined into a short section (10 feet) of 4‐inch corrugated HDPE pipe and discharged into the existing adit water collection pond. See Figure 2‐4 for the layout of the treatability study post construction.
Because the BCR barrels were operated near the main site access road, security from potential vandalism was incorporated into the implementation. Foliage was gathered from the nearby forest area and used to cover the large main feed tank obscuring its view from the road. Straw bales were stacked in front of the pretreatment barrels and the BCRs, held in place with T‐posts, obscuring the direct view of the barrels from the road. 2.4 System Startup, Operation and Maintenance, and Shutdown This section provides the details of the system startup procedure, the operation of the treatability study with details and schedule of the maintenance performed, as well as the shutdown and deconstruction of the system. 2.4.1 System Startup The pilot‐scale system was installed over several days from June 17 through June 21, 2013. The treatment system was initially constructed as described above. Substrates were added to each barrel on June 19. MIW was added to the barrels from June 19 through 21 to hydrate the media. Untreated MIW was added to the pre‐treatment barrels and BCR 1 and 2. MIW added to BCR 3, 4, 5, and 6 was first treated with limestone to raise pH to above 5. Water was added over the course of 3 days until a static level of 30 inches was achieved. Water from the barrels was then recirculated on June 21. ChitoRem® barrels flowed approximately 1 liter per hour (L/hr) in this early stage, and 9.5 to 11.4 L were recirculated in each. BCR 1, 3, and 5 demonstrated a capacity to keep up with design flow from initial saturation, and 19 L was recirculated in each. SAPS pre‐treatment barrel did not flow during the construction window. The saturated media would then sit for 2 weeks to incubate prior to initiation of flow through.
On July 3, SAPS was investigated to evaluate prior to the anticipated July 8 system flow launch date. The SAPS barrel showed no sign that any flow had occurred from the drain manifold while it sat for 12 days. The water level in the barrel had dropped, most likely a result of media saturation and not effluent discharge. MIW was added to bring the water level up to the brim of the barrel. The static head within the barrel from the water surface to the highest point of the drainage manifold was not enough to induce flow. The lid to the barrel was sealed air tight, and a 5‐gallon bucket was filled with MIW and suspended several feet above the barrel to imitate the potential head from the head tanks. A length of 1 inch braided PVC tubing was used to create a siphon from the suspended bucket to the inlet of the sealed SAPS barrel. The induced head was sufficient to induce flow through in the SAPS barrel to 7.6 L/hr, a flow sufficient for design pre‐treatment flow of 14 L every 3 hours. At this time, approximately 19 L were recirculated back into the tank.
On July 7, during the finalization of the treatability system plumbing, it was discovered that the junctions in the line to split the flow between BCRs 1 and 2, 3 and 4, and 5 and 6 were not sufficient to divide the flow evenly between the three pairs. A fix was developed to ensure a more accurate distribution of flow. To do this, timer valves were installed after the split T on the even BCR barrel side of each pair. The split lines were angled such that the even BCR side with the flow valve was secured at an elevation below the split and the line going to the odd BCR side was elevated from the T. When the flow valve opened, all the flow traveled down gradient to the even numbered BCRs. When the flow valve closed, all flow traveled
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up from the split T in the line and into the odd numbered BCRs. Figure 2‐5 shows this modified configuration between BCR 1and BCR 2. This new configuration staggered the flow, rather than split the flow, and therefore the head tank and timing regime was adjusted to accommodate the adjustment. Considering that all the head tank flow would be going to one BCR per batch from the pre‐treatment for BCRs 3 and 4 and BCRs 5 and 6 or directly from the head tank for BCRs 1 and 2, the timing of the head tank batches was reduced from 3 hours to 2 hours, and the volumes were reduced from 14 L to 9.3 L by inserting a stand pipe in the tank to only allow half the volume to drain each batch. The timer on the feed tank was also adjusted accordingly to fill the head tanks every 2 hours instead of 3 hours. The timing on the BCRs was then set to have the odd‐numbered BCRs receive flow for 2 hours while the even numbered BCRs received no flow while the timer valve was closed. The even‐numbered BCRs would receive flow for 2 hours while the odd‐numbered BCRs received no flow when the timer valve was open. The new configuration maintained the same over all flow rates to both the pre‐treatment barrels and the BCRs. Flow through was initiated on July 8 with a modified flow through configuration. Once design flow was established through all of the barrels, the system was run for approximately 40 hours prior to the first sampling event.
Following a 2‐week incubation period and approximately 40‐hour flow through period, the first round of samples was collected on July 10, 2013 at the Formosa Mine Treatability Site. Sampling activities are described in Section 2.5.1. 2.4.2 Operation and Maintenance Maintenance on the treatment system was conducted during each sampling event. These activities included checking the system for leaks or clogging and replacing the timer valve batteries. A bullet summary of maintenance activities is provided below.
During the July 22 through 23 round 2 sampling event, multiple issues were observed in regards to flow through the system. The effluent vent coming from the SAPS barrel was overflowing because of a blockage in the line between the pre‐treatment barrel and the BCRs. The blockage in the line between the SAPS and BCR 3 and 4 was cleared by shaking the line vigorously. Visual observations confirmed that the blockage had been dislodged.
. The ChitoRem® pretreatment barrel was overflowing from the vent in the lid, indicating that the flow through the media is not able to keep up with the batch rate from the head tanks. The issue was resolved by sealing the lid vent, similar to the SAPS barrel, to increase the head in the system to induce greater flow through the media. After the resolution, both pre‐treatment barrels were able to maintain design flow during the sampling event on July 23.
. The ChitoRem® BCRs (2, 4, and 6) were all observed to be flowing at a rate less than design flow and were not able to receive the full slug of water during the 2‐hour interval. This resulted in flow leaking out the lid vents in the even numbered BCRs and caused water to back up into the even numbered BCRs’ inlet port; therefore, BCRs 1, 3, and 5 were receiving extra flow. BCRs 1 and 5 were receiving flow greater than the design criteria. Although BCR 3 was receiving extra flow during BCR 4 flow periods, it is unclear if it was operating above or below design flow because of blockage in the flow line coming from the pre‐treatment barrel. The issue with flow at BCR 2 with no pretreatment was resolved by installing a flow regulator plug in the head tank feeding BCRs 1 and 2. Based on previous investigations, it was determined that flow in BCRs 4 and 6 may improve over time, and therefore the BCRs were to be observed after 2 weeks to determine whether improvement had occurred.
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. Batteries were changed in all timer valves.
During the August 5 and 6 round 3 sampling event, it was observed that the SAPS effluent vent was overflowing again, and ChitoRem®‐containing BCR barrels 2, 4, and 6 were overflowing from their lids. The SAPS effluent line was cleared by shaking and this time buried to prevent any potential of photosynthesis contributing to the blockage. Considering that the flow was not observed to be improved in BCRs 4 and 6; the following measures were taken to improve and maintain system flow:
. The drainage manifolds on each barrel were lowered to a height of 2 inches above the measured substrate surface, a decrease of approximately 4 inches for each manifold. The decrease in height was intended to increase the pressure head between the water surface in the barrel and the exit port. Maintaining a height of 2 inches above the media surface ensured that if flow did increase, there would not be a risk of exposing the media to air and potential drying.
. An extra timer valve was installed on the odd numbered BCR of the influent split. The timer valves on the odd numbered BCR side were set to be closed during flow to the even numbered BCRs. The purpose of this modification was to prevent flow intended for even numbered BCRs from spilling over into odd numbered BCRs.
. Batch volumes for all three head tanks reduced by half from 9.3 L to 4.7 L.
. After reduction of flow, BCRs 4 and 6 were still overflowing and not keeping up with the new lower flow. Stand pipes were installed on BCRs 4 and 6 lid vents to allow pressure head to build without losing water out of the lid. Elevated water in the standpipe after the timer valve closes also helped keep increased pressure head in between batches.
. It was determined to reassess flow issues in 2 weeks to give the new adjustments time to improve flow.
. Batteries were changed in all timer valves.
During the August 19 and 20 round 4 sampling event, the timer valve for the main feed tank was found to be locked open and was continuously filling the head tanks. Flow issues were also observed with the ChitoRem® pretreatment barrel passing approximately half of its volume each batch, and BCRs 4 and 6 were overflowing from their standing pipe vents. Measures taken to improve the observed flow issues were as follows:
. The feed tank timer valve was replaced. It is unknown how long the timer valve had malfunctioned since the last maintenance check 2 weeks prior. However, it would not have much effect on BCR 3 through BCR 6 considering the SAPS pretreatment head tank took almost the full 90 minutes of its batch window to empty the head tank, and the ChitoRem® pretreatment only drained half of its head tank volume during its batch window. The head tank for BCRs 1 and 2 took approximately 5 minutes to empty, and the timer valve was set to remain open for 15 minutes each batch and therefore may have been receiving 3 times the flow during the valve malfunction.
. Although the effluent line in the SAPS was not plugged at this time, it was replaced with new tubing to help prevent future plugging issues. Flow issues persisted with the ChitoRem® pretreatment and BCRs 4 and 6 despite previous efforts to improve flow.
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. Batteries were changed in all timer valves.
During the September 3 through 6 round 5 sampling event, the ChitoRem® pretreatment barrel was observed to be passing approximately 2/5 of the head tank volume per batch, and all three ChitoRem® BCRs were overflowing. Measures taken to address flow issues and maintenance follow:
. All BCR and pretreatment barrels were back purged with argon gas. The purpose was to dislodge any potential blockages that may be accumulating on or within the drainage manifold at the bottom of the barrel. All barrels, both ChitoRem® and woody substrate, were purged to ensure system comparability. To purge, the lid was removed from each barrel, and tubing affixed to an argon tank was attached to the end of the barrel’s effluent line. Argon gas was applied at 10 pounds per square inch (psi) for as long as it took for bubbles to appear at the surface, approximately 10 to 20 seconds. In the woody substrate BCRs, it was observed that multiple bubble flow paths were formed. However, in the ChitoRem® barrels, bubbles emerged from only one or two most likely preferential flow paths.
One day after the barrels were purged, flow rates were measured at the effluent of the ChitoRem® BCRs. The measured flows were 0.4, 0.7, and 0.2 L/hr from BCRs 2, 4, and 6, respectively. Considering that the targeted flows were 1.2 L/hr for the BCRs, it was determined that the flow issues observed were not related to blockages in the drainage manifold but instead related to blockages in the substrate column.
A final strategy was implemented to attempt to improve the ChitoRem® barrels by rebuilding them to increase permeability. The rebuild was conducted after the round 5 (September 4, 2013) sampling event was completed. To rebuild the ChitoRem® barrels, the ChitoRem® media were removed and mixed to bring the pea gravel content up by 35 percent. The barrels were then packed again back to their original volume, and therefore some media was discarded. For each barrel, water overlaying the substrate was decanted and saved to be used to mix in with the mixture when repacking the barrel to ensure that the media are saturated. Prior to each rebuild, undisturbed sediment cores were taken and sent to a geotechnical laboratory for grain size distribution and permeability analysis. The following bullets summarize the observations of the rebuild from each barrel.
. ChitoRem® Pretreatment: 33 gallons of media were removed and mixed with additional pea gravel resulting in a 35 percent increase in pea gravel. Thirty‐six gallons of the new mixture were then replaced back into the barrel. The substrate surface height after the rebuild was measured to be 23.5 inches. A cross section of the media prior to removal showed an orange iron oxide rich layer on the substrate surface, which overlaid a 1‐inch gray material layer followed by a 4‐ to 6‐ inch layer of very black material. These top layers were very saturated with moisture. Below the top layers, the media were mostly black with several grey patches and although the lower media were wet, they were not saturated with liquid as the top layers were, except for along the sides. The gravel at the bottom was stained black.
. BCR 2: 27 gallons of media were removed and mixed to increase pea gravel by 35 percent. Thirty‐ seven gallons of the new mixture were replaced back in the barrel. The substrate surface height after the rebuild was measured to be 23.5 inches. A cross section of the media prior to removal showed the top 3 inches of material was black and saturated with liquid. Below the top layer, the ChitoRem® material looked grey, similar to the color during installation, and was wet but not saturated. The gravel in the bottom was not stained black.
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. BCR 4: 33 gallons of media were removed and mixed to bring pea gravel up by 35 percent. Thirty‐ five gallons of new mixture were replaced back in the barrel. The substrate surface height after the rebuild was measured to be 23.5 inches. A cross section of the media prior to removal was seen to have a 4‐ to 6‐inch black layer saturated with liquid on top, with a grey layer below that was wet but not saturated and appeared to be the original ChitoRem® color from installation. The gravel at the bottom was not stained black.
. BCR 6: 34 gallons of media were removed and mixed to bring the pea gravel content up by 35 percent. Thirty‐five gallons of new mixture were replaced in the barrel. The substrate surface height after the rebuild was measured to be 23.5 inches. A cross section of the media prior to removal was observed to have a gelatinous black surface layer that was 4‐ to 6‐inches thick. Below the upper layer was a sandy grey media layer that was wet but not saturated. The gravel at the bottom was not stained black.
Flow measurements of the ChitoRem® pretreatments a day after the rebuild showed flows of 0.25, 0.1, and 0.3 L/hr for BCRs 2, 4, and 6, respectively. The flow issue did not initially appear to be resolved with the rebuild, but time was needed for the newly mixed media to stabilize. The ChitoRem® pretreatment was passing the full batch flow through. Stand pipes were installed in the ChitoRem® BCR vents. Batteries were changed in all timer valves.
During the September 10 site visit, the ChitoRem® BCRs all showed signs that they had been overflowing out of the standing pipe vent. A flow test showed very little flow from the ChitoRem® BCRs, approximately 0.075 L/hr for all three.
During the September 16 and 17 attempted sampling event, it was discovered that the adit portal had stopped flowing and the treatability study was no longer receiving flow of MIW. The low flow was not a naturally occurring event, but was related to an engineering evaluation that involved withdrawal of water from MW‐24, which is a monitoring well that extends into the internal workings of the adit. At this point, the water from the adit portal ceased flow to the treatability study. The pressure transducer at MW‐24 was downloaded to determine water elevation and recovery time. The well had been drawn down 9.1 feet during the pump test and had recovered 3.1 feet in 4 days. Batteries were changed in all timer valves.
During the September 23 observational visit, the adit was confirmed dry.
During the September 26 visit, the adit was confirmed dry. The pressure transducer that had been in MW‐24 had been removed by the drillers. A new pressure transducer was installed, and the water level had recovered to within 2.26 feet from the pre‐pump test elevation.
During the September 30 through October 1 attempted sampling event, the adit was confirmed dry. The pressure transducer at MW‐24 was downloaded, and the water level had recovered to within 1.51 feet of the pre‐pump test elevation. Batteries were changed in all timer valves.
During the October 11 observational visit, the adit was confirmed dry.
During the October 16 site visit, the adit portal had standing water but not yet enough to start flowing into the treatability system. Considering the treatment barrels had been sitting stagnant for a month, there was a concern that methanogens had established themselves within the ChitoRem® barrels, making it unlikely that SRB populations would recover. If indeed the flow did start back up again, the established methanogen population most likely would out‐compete the SRB. A Photovac MicroFID IS
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Flame Ionization Detector (FID) methane detector and a RAE Systems, Inc. Q‐RAE Plus Four‐Gas Monitor, which measures hydrogen sulfide (H2S), were used to detect concentrations of the two gasses in the headspace of each barrel to validate the methanogen colonization concerns. Headspace concentration results are listed in Table 2‐1. All ChitoRem® BCRs had methane concentrations above the upper limit of the instrument, 3611 milligrams per cubic meter (mg/m3). In six of the eight barrels (75 percent), the methane concentrations exceeded the threshold of the measuring instrument. 2.4.3 System Shutdown The pilot‐scale treatment system was shut down on October 24. Undisturbed core samples were collected from each of the three ChitoRem® BCRs and the ChitoRem® pretreatment barrel. The barrels and the media were transported to a secluded location on the Formosa Mine encapsulation mound. To move the barrels, the media were transferred into 5 gallon buckets and transported with the empty barrels to the storage location. As each barrel was dug out, a cross section was cut into the media to make observations. The rebuild ChitoRem® barrels were essentially identical, each having a 3‐ to 4‐inch saturated layer at the top with wet but not saturated material below. All ChitoRem® barrels were uniformly black throughout. In all the ChitoRem® barrels, the standing water was very black and turbid. The woody substrate BCRs 1, 3, and 5 were not as uniform. BCR 1 had an orange biofilm layer on the substrate surface that was covered in an algae layer; beneath these thin surface layers was a thin 1‐inch grey layer over a black media that extended to the bottom of the barrel. BCR 3 had an orange biofilm on its substrate surface overlaying a 3‐inch layer of dark grey material, with black substrate below in the rest of the column to the bottom. The top 3 to 4 inches of material were black in BCR 5, overlaying grey material down to the bottom of the barrel. The SAPS pretreatment barrel had lost its permeability during the stagnation period; however, after digging through the top 5‐inch manure layer, the overlying water rapidly drained from the barrel. The top manure layer of substrate was covered with algae, and the manure itself was a dark green and looked like fresh manure. There was a black layer approximately 1‐inch thick where the manure and limestone layers merged. In all of the woody substrate BCRs and SAPS, the standing water was clear and transparent. Once transferred to the encapsulation mound, the media were placed back into the barrels, and they were sealed and covered with a large tarp. The rest of the plumbing and miscellaneous parts were disposed of at a local landfill. 2.5 Pilot Study Sampling This section summarizes the details and schedule of the samples collected during the treatability study, including ancillary data collected at the adit portal that can be used to support the analysis of the study. 2.5.1 Sampling Activities Water samples were collected from each of the six BCR barrel effluent sampling ports, from the two pretreatment barrel effluent sampling ports, and from the influent MIW feed tank sampling port. These nine samples were collected every other week throughout the testing period for the first five rounds of sampling. There had been nine sampling events scheduled; however, after round 5, a pumping test on September 12, 2013 at MW‐24 dewatered the adit, which discontinued the adit MIW flow for the remainder of the scheduled treatability study. Therefore, a total of five sampling events were performed, the samples of which are outlined in Table 2‐2 with the field activity timeline outlined in Table 2‐3.
All intended samples were taken with the exception of sulfide in round 1 and mercury via analysis method 7470 after round 2. Initially, sulfide was to be analyzed in the field with a colorimetry kit; however, the ultra‐high turbidity encountered in the effluent samples was out of the kit’s range. For round 2, a modified sulfide kit was obtained with reagents appropriate for the high turbidity. A test was
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performed comparing field measurements to preserved and unpreserved samples analyzed in a laboratory. The preserved samples analyzed in the laboratory were consistently higher than both the unpreserved laboratory analyzed samples and the field measured samples. After round 2, only preserved samples for laboratory analyzed sulfide were collected.
There were three planned effluent sample collection events from all six BCRs to conduct low level mercury and methylmercury analysis by EPA Manchester Environmental Laboratory (MEL). The first round of trace mercury sampling occurred during the fourth round of regular sampling. A second and third round of mercury sampling would have taken place on rounds 6 and 9; however, these events were cancelled after the MIW flow was interrupted.
During round 4, samples were collected at the Formosa Adit under EPA sample plan alteration form (SPAF) number 2 to the OU2 Data Gaps Assessment and Sampling and Analysis Plan (SAP) Addendum, September 2012. Under this SPAF, the Formosa Adit was sampled for trace mercury analysis, and these results are used in this study as a mercury inlet concentration for the treatability study. Results are being used to investigate the effect that the sulfate‐reducing bacteria have on the methylation of inorganic mercury to methylmercury, whether or not the ChitoRem® media is a source of mercury, and whether or not this is a concern at this site with this type of treatment technology. 2.6 Deviation from the Pilot Study Work Plan (PSWP) and Quality Assurance Project Plan (QAPP) This section details the deviations from both the work plan and the QAPP that occurred during the treatability study. 2.6.1 Deviation from PSWP and QAPP A primary deviation from the QAPP was the cessation of the study after 10 weeks. There were 5 rounds of sampling conducted, though 8 events were planned.
The elevated turbidity of the sample matrix in the treatability study effluent proved to be challenging to conduct field measurement of sulfide using method 8131, USEPA Methylene Blue method. During the round 1 sampling event on July 10, the turbidity was found to be too high for the standard kit. A remedy to the turbidity issue is to utilize a bromine water digest, which was not available in the field at this time. Sulfide data from field testing, ORD analysis of unpreserved sample, and ORD analysis of a sample with sodium hydroxide and zinc acetate to a pH greater than 12, were collected and compared in sampling event 2. For all events after event 2, sulfide analysis was performed only by the ORD laboratory.
The pH of the nitric acid preserved metals samples was checked in the field to ensure all samples had a pH less than (<)2. Extra nitric acid was used when necessary to achieve this pH in the field.
Split sampling for samples through the Contract Laboratory Program (CLP) was added to the scope, and samples from round 5 were sent to Chemtech Consulting Group, Mountainsides, NJ, in addition to ORD. The complex nature of the samples and the relatively low level of analytical documentation in regards to raw data, calibration, and matrix spikes resulted in a perceived need by the EPA for data with elevated quality assurance/quality control (QA/QC) documentation. In addition, CLP laboratory Chemtech Consulting Group, Mountainsides, NJ reports detected mercury to their method detection limit (MDL) of 0.011 µg/L, compared to the ORD method reporting limit (MRL) of 0.139 µg/L. The CLP contract required quantitation limits (CRQLs) for some of the other analytes of interest, which are also lower than the ORD MRLs, see appendix B data evaluation memo.
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Mercury was analyzed by the ORD laboratory for events 1 and 2 but was not for events 3 through 5, because mercury by SW846 method 7470, cold vapor atomic absorption (CVAA) was not detected in any sample in round 1 or 2. However, the CLP laboratory analyzed mercury in round 5, thus only rounds 3 and 4 did not provide mercury data by CVAA. However, for round 4, samples were collected for low level mercury and methyl mercury analysis. BCR effluent samples were submitted to the EPA laboratory MEL, for analysis of low level mercury and methylmercury by methods 1631 and 1630, respectively. This sampling in round 4 was a deviation to the original QAPP which called for low level mercury analyses in rounds 6, 7, and 8. This deviation was made for the sampling to coincide with Formosa environmental sampling being performed at that time under EPA SPAF QAPP Addendum #2 to the OU2 Data Gaps Assessment and Sampling and Analysis Plan Addendum, September 4, 2012. Under this effort, the Formosa Adit was sampled for low level mercury and methyl mercury analysis by Battelle at Pacific Northwest National Laboratories (PNNL) in Sequim, WA. By using results from this sampling effort, low level mercury data for the influent and the effluent samples will be available for round 4. Data is expected to be available from MEL for the BCR effluent samples in March 2014.
There are no mercury data from the pretreatment effluent for events with low level mercury analyses. The absence of mercury measurements for round 3, and for the pretreatment locations from round 4 did not compromise the study objectives because the mercury data collected, inclusive of the low level analyses and the CVAA analyses, were sufficient to meet objectives.
At present, there is a lack of information on low level total‐mercury (THg) and methylmercury (MeHg) concentrations at the Formosa Superfund Site. Based on mineralogy of the ore body and surrounding material, mercury was not believed to be present at sufficient concentrations to justify low level mercury analysis. That conclusion is still believed to be the case; however, the potential for methylation of mercury through sulfate‐reducing bacteria may not have been considered when the project QAPP was originally prepared. MeHg sampling has not occurred previously at the site. The reason for collecting these data is to measure THg and MeHg from waters emanating from the mine area with low detection limits (i.e. EPA 1630 and 1631— ≤0.5 nanograms per liter [ng/L]). The Formosa low level mercury environmental sampling plans presented in the SPAF QAPP Addendum #2 as noted above. Samples were collected from environmental locations at the site, including the Formosa Adit. Samples were collected in May, in August coinciding with round 4 of the treatability study, and October. In addition, several additional parameters that have been shown to influence mercury (Hg) cycling (organic carbon, anions, ammonia, dissolved metals, sulfide, total suspended solids, pH, alkalinity, and volatile fatty acids), will be analyzed from these SPAF #2 samples. These data are being used in conjunction with trace mercury samples collected from the treatability study BCR effluents in round 4.
Several adjustments were made in the system design outlined in the treatability study work plan to address issues with the system flow. During construction of the system, it became apparent that a T‐split would not accurately regulate a split flow. This problem was ultimately resolved by installing a flow timer on both branches downstream of the T‐split, and adjusting the flow regime so that flow was alternated between BCR barrels instead of split between them (see Section 2.4.1).Throughout the test, the flow through the ChitoRem® barrels steadily decreased. Attempts to resolve this issue included reducing the design flow by half, lowering the drainage manifold 4 inches, adding stand pipes to the BCR lid vents, and back flushing the barrels with argon gas. These measures did not improve flow, so a final measure was implemented, which involved increasing the pea gravel content of the ChitoRem® mixture by 35 percent (see Section 2.4.2). MIW from the adit ceased flowing after the pea gravel amendment, and it was unclear what the effectiveness was of that measure.
2‐11 Section 2 Pilot Study Methods and Sampling
The permeability, density, and specific gravity were tested to support evaluations of retention time and substrate mix design. Undisturbed core samples from ChitoRem® reactors 2, 4, and 6 and pretreatment were collected and tested according to the following methods after the system rebuild and during system shutdown:
. American Society for Testing and Materials (ASTM) D1 587 ‐ Standard Practice for Thin‐Walled Tube Sampling of Soils for Geotechnical Purposes
. ASTM D854 ‐ Standard Test Methods for Specific Gravity of Soil Solids by Water Pycnometer
. ASTM D 5084 ‐ Standard Test Methods for Measurement of Hydraulic Conductivity of Saturated Porous Materials Using a Flexible Wall Permeameter.
Collection of samples during events 6 through 9 was not possible because flow from the adit portal had stopped and no longer fed the treatment system intake. When sample collection from event 6 could not occur, event 9 was added, but ultimately no sampling occurred after event 5 other than the OU2 Data Gaps trace mercury sampling that occurred on October 23 at the Formosa Adit.
The headspace in all eight reactor barrels was measured for hydrogen sulfide and methane gas using a RAE Systems Multi Photoionization Detector (PID) 4‐Gas Monitor with PID and a Photovac MicroFID IS Flame Ionization Detector, respectively, on October 16, 2013. At this time, the barrels had been sitting with stagnant MIW for over a month, and a determination needed to be made as to whether the system could be restarted if the adit MIW began to flow again. Elevated presence of methane in the ChitoRem® reactors might indicate that SRB could be out competed by methanogens and not be able to reestablish a productive colony.
2‐12
Section 3 Evaluation Criteria, Results, and Discussion
This section describes the results, analysis, and discussion of the treatability study data. The evaluation criteria are presented in Section 3.1. The results are presented in Section 3.2. The comparison among the six treatment trains and operation and maintenance considerations are discussed in Section 3.3. 3.1 Pilot Study Evaluation Criteria Several criteria are used to evaluate the effectiveness and performance of the pre‐treatment systems, the BCRs and the overall treatment process. 3.1.1 MRE The metals removal efficiency (MRE) was the major metric used as an indicator of treatment effectiveness. Seven target metals of interest are identified because of their low surface water discharge benchmarks; these include cadmium, chromium, copper, lead, nickel, silver, and zinc. Other metals, such as arsenic, mercury, aluminum, and iron, are also important components for the evaluation. Achieving consistent MRE of target metals was a specific goal of the treatability study, and the target MRE for the pilot‐scale treatability study was 90 percent. Note, silver was generally below MRL throughout the sampling events. Therefore, no further discussion on silver will be presented. Low level BCR effluent mercury data are not available at the time of preparation for this technical memorandum and will be included in the final report. The data is expected to be available after March of 2014.
MRE for each treatment system is expressed as a percent of the concentration decrease between the MIW influent and BCR effluent. In cases where concentrations were below MRLs, the MRL was used to calculate the MRE. ORD did not report values below the MRL In Table 3‐4, MRE values qualified with a greater than symbol (>) indicate that the effluent was below MRL and the actual MRE value is greater than was is reported. MRE values qualified with a less than symbol (<) indicate that the influent was below MRL and the actual MRE is less than what is reported. MREs were not calculated if both influent and effluent were below MRL. The MIW collected from the feed tank overflow was used as the influent concentration for all BCRs, with and without pretreatment. Pretreatment and BCR pairs are considered a treatment system when calculating MREs. Standalone barrel removal efficiencies of each pretreatment and BCR pairs are evaluated and reported separately from the MRE evaluation of the full system. 3.1.2 Water Quality The changes in groundwater chemistry other than metal concentrations were evaluated using pH, alkalinity, sulfate, and ORP water quality parameters. These water quality parameters are indications of the groundwater geochemistry that are relevant to the precipitation of metals and the activity of SRB. The water quality of BCR effluent would impact the required post BCR treatment process. Furthermore, the effluent water quality parameters (including metals) were compared to hardness‐ corrected surface water quality values. This comparison was made to support future discussions and evaluation regarding potential post BCR treatment and discharge locations (Table 3‐1). The effluent
3‐1 Section 3 Evaluation Criteria, Results, and Discussion
for the treatability was not discharged to surface water because the drainage for the Formosa Adit flows to a drainfield in alluvial soil and shallow groundwater at least 500 feet upgradient from surface water. Recent ecological evaluations determined there are no aquatic life receptors in the surface water zone comprising the rocky seeps area where groundwater from the vicinity first discharges. Therefore, the surface water quality standards are presented for comparison, and are not applicable to the study nor were they performance objectives for the system. 3.1.3 Pre‐Treatment and BCR System Operation and Maintenance Considerations The performance of each pre‐treatment system and each BCR system in terms of maintaining flow and designed retention time, precipitation of solid, changes of porosity, and longevity will be discussed. 3.2 Results and Discussion Field parameters; analytical results from the influent (feed tank and adit portal) and each treatment system (pre‐treatment barrel or BCR barrel); and the permeability, density, and specific gravity of the ChitoRem® substrate are presented here. All analytical data presented here have been validated and deemed useable. Dissolved metals are presented as the focus of this final technical memorandum with respect to MRE and comparison to screening levels considering they are more labile and readily transported downstream. Results of total metals are not discussed but can be found in Table 3‐2. A trace mercury speciation analysis was performed on the inlet and effluent of the BCRs on the total unfiltered sample during round 4. These mercury results are presented below and are important to determine the effect of the SRB activity on methylmercury effluent concentrations. All data as qualified was considered usable as discussed in Section 3.3 and Appendix B. 3.2.1 MIW Influent Laboratory results of samples collected from the effluent line of the feed tank representing the MIW influent to the pilot‐scale treatability study systems are summarized below. Table 3‐2 and Figures 3‐1 to 3‐21 present the results.
Field Parameters Field parameters are presented in Table 3‐3 and Figures 3‐1 to 3‐6.
The MIW pH ranged from 3.07 to 3.37 su, DO ranged from 0.05 to 2.04 milligrams per liter (mg/L); ORP was greater than 320 millivolts (mV), and conductivity ranged from 1,366 to 1,541 microSiemens per centimeter (µS/cm) in the five rounds of sampling (Table 3‐1). The field parameters did not show large variation of influent DO and pH. Rain events occurred between sampling events 3 and 4 and between sampling events 4 and 5, which might have impacted the MIW water quality. However, no significant water quality variation was observed.
Metals The analytical results for raw MIW from the adit are discussed for each target metal and then other metals of elevated concentration in the MIW. Discussion will focus on the dissolved concentrations for metals.
Target Metals . Cadmium (Cd) ranged from 0.142 to 0.194 mg/L.
. Chromium (Cr) ranged from 0.0112 to 0.263 mg/L.
3‐2 Section 3 Evaluation Criteria, Results, and Discussion
. Copper (Cu) ranged from 3.832 to 5.471 mg/L.
. Lead (Pb) ranged from below the MRL of 0.017mg/L to detected values up to 0.041 mg/L.
. Nickel (Ni) ranged from 0.027 to 0.049 mg/L.
. Zinc (Zn) ranged from 63.8 to 72.5 mg/L.
Other Major Metals . Aluminum (Al) ranged from 12.4 to 14.2 mg/L.
. Arsenic (As) ranged from below the MRL of 0.036 mg/L to a detected value of 0.039 mg/L in round 5.
. Calcium (Ca) ranged from 98 to 112 mg/L.
. Cobalt (Co) ranged from 0.012 to 0.019 mg/L.
. Iron (Fe) ranged from 148 to 171 mg/L.
. Manganese (Mn) ranged from 2.09 to 2.19 mg/L.
Mercury (Round 4) . Total Mercury (THg) was 2.18 ng/L.
. Methylmercury (MeHg) was below the MRL of 0.05 ng/L.
Wet Chemistry Parameters There was no alkalinity in the influent MIW with the presence of low pH (~3.0 to 3.5). Sulfate concentrations increased from 1,765 mg/L at the beginning of the study to 2,004 mg/L during the last round of sampling.
Summary Overall, the water quality data of the MIW were generally stable during the pilot study duration, with a slight increase in sulfate concentration at the end of the study. There was no obvious indication of wet weather impact on the water quality even though precipitation increased at the end of the study in August 2013. Results from round 4 suggest that the Formosa Adit is not a significant source of mercury, with THg values below the mean found in unmined basins of 2.96 ng/L (Scudder et al. 2009) and with MeHg below the MRL of 0.05 ng/L. The term unmined basins refers to watersheds that are either used for agriculture, urbanized, or undeveloped but no history of gold or mercury mining activity. 3.2.2 BCR Barrels 1 and 2 The purpose of the installation of BCR 1(woody substrate) and BCR 2 (ChitoRem®) was to compare the performance of the two substrates in both their ability to increase pH and induce a greater than 90 percent MRE with raw non‐pretreated MIW. The results from the non‐pretreated BCR systems will be compared to the performance of identical treatment media with both a SAPS and ChitoRem® pretreatment step. Table 3‐2 and Figures 3‐1 to 3‐21 present the results.
Field Parameters Field parameters are presented in Table 3‐3 and Figures 3‐1 to 3‐6.
3‐3 Section 3 Evaluation Criteria, Results, and Discussion
The field parameters of pH, conductivity, ORP, temperature, and DO are broad indicators of the BCR performance. The pH decreased in BCR 1 after round 1 from 6.3 to 5.4 su. This drop coincides with observations that BCR 1 was receiving overflow from BCR 2 and therefore received more than the 2.3 L/hr of the acidic MIW, potentially overwhelming the buffer capacity of BCR 1. The pH increased in round 4 to 5.8 su, which also coincides with the installation of an extra flow timer that prevented the overflow from BCR 2 to BCR 1 and reduced the design flow by half, further reinforcing the hypothesis that the observed pH fluctuation was related to flow. The pH dropped again in round 5 to 5.6 su, which coincides with an increase in ORP and several metal concentrations. Considering there was very little variation in the raw MIW throughout the test, BCR 1 was losing its buffering capacity by round 5. BCR 2, by contrast, maintained a pH that fluctuated within 0.3 units around 6.5 su. The pH dipped the most in round 3 at 6.2 su but then steadily increased to 6.6 in round 5. The increase occurred after the flow was decreased by half. BCR 2 appears to have residual buffer capacity after the first five rounds of sampling and did not drop below a pH that could inhibit SRB activity, pH < 4 su (EPA 2006).
Conductivity was higher with both BCRs as compared to MIW, 4,000 and 36,000 µS/cm in BCR 1 and 2, respectively, compared to 1,500 µS/cm in the adit. Initial flushing of soluble components from the substrate is common in these types of BCRs thereby elevating the conductivity. After round 1, conductivity in BCR 1 stabilized to a level similar to the MIW. BCR 2 dropped significantly over the first three rounds; however it started out an order of magnitude higher than BCR 1 and remained elevated from MIW for the entire five rounds of the test. Elevated conductivity of this magnitude was observed in the effluent of ChitoRem® BCRs at another similar MIW pilot scale treatment test performed by EPA in 2013 (CDM Smith, 2013a).
Temperature in the effluent of both BCRs 1 and 2 tracked within about 1oC of each other, slowly dropping from 21oC in round 1 to 15oC in round 5. The drop in temperature tracks with the falling air temperatures and the shortening of days as time moved into late summer. These temperatures do not drop below the level that have been demonstrated to inhibit SRB, < 6oC (Neculita and Zagury 2008; EPA 2006).
Reducing conditions in BCRs 1 and 2 were initially low, with ORP values of ‐150 and ‐200 mV, respectively, in round 1. ORP increased in BCR 1 from round 2 through 4 to approximately 0 and then increased again to 50 mV in round 5. BCR 2 was poised just above ‐200 mV for the majority of the test, with the exception of a temporary drop in round 4 to ‐300 mV. Reducing conditions in BCR 1 effluent never dropped to below the ideal conditions for sulfate reduction, < ‐200 mV (EPA 2006). BCR 2 effluent remained close or within the optimal redox conditions for SRB activity throughout the five rounds of the test.
A malfunction with the DO probe was discovered in round 4 when DO readings were excessively high. A new probe was acquired in round 5 that showed results mostly under 0.5 mg/L, and validated the concerns that the previous probe had been malfunctioning.
Metals The analytical results for BCR barrels 1 and 2 are discussed for each target metal and then other metals of elevated concentration in the MIW. Discussion will focus on analysis of dissolved concentrations for metals for all five rounds and concentrations of THg and MeHg from only round 4. Observations of MRE ranges (Table 3‐4) and comparison to screening benchmarks (Table 3‐1) are as follows.
3‐4 Section 3 Evaluation Criteria, Results, and Discussion
Target Metals . Cadmium (Cd) removal was at 90 percent or greater in BCR 1 until round 5 where it dropped to 80 percent and ranged from the MRL of 0.002 mg/L to 0.029 mg/L. Cd was detected at 0.016 mg/L in the first round of sampling in BCR 2 and then decreased below MRLs in the last three rounds of sample collection. The MRE stayed at 100 percent from round 3 to round 5. Ninety percent performance criteria targets for dissolved Cd in effluent were achieved in BCRs 1 and 2 with the exception of round 5 in BCR 1 when MRE dropped to 80 percent. Although BCR 2 made its performance target, both BCRs 1 and 2 were above the potential water quality benchmarks of 0.00035 mg/L.
. Chromium (Cr) removal efficiency started out at 100 percent in round 1 but then dropped to a range of 19 to 30 percent from round 2 to round 5. Cr was detected in round 1in BCR 2, with an MRE of 86 percent, and decreased to below the MRL of 0.024 mg/L from round 2 to round 5. Performance criteria targets for dissolved Cr in effluent were not achieved in BCR 1 after round 1. BCR 2, with the exception of round 1, did achieve the target 90 percent or greater removal. BCR 1 did not achieve discharge benchmark of 0.111 mg/L in rounds 2, 3, and 4 while BCR 2 was able to meet the discharge benchmark throughout the entirety of the test.
. Copper (Cu) was nearly removed from the waste effluent from BCR 1 in round 1 and then stabilized at an MRE at just over 90 percent for the remainder of the test. Although a small detection of Cu was made in round 1, BCR 2 MRE was nearly 100 percent for the entirety of the test. Both BCR 1 and 2 achieved the target 90 percent reduction. Although BCR 1 met the target reduction, its effluent was above the potential water quality benchmark of 0.012 mg/L. BCR 2 was able to meet the potential water quality benchmark with the exception of round 1. The removal mechanisms in BCR 1 most likely were not dominated by adsorption considering the relatively high influent Cu concentration 4 to 5 mg/L. The removal was most likely mediated by precipitation of oxy‐hydroxides and carbonates. Precipitation by sulfate reduction dynamics most likely was not a factor in BCR 1 as there did not appear to be an ideal SRB environment, i.e., higher ORP, higher sulfate, and lower sulfide effluent in that barrel. A decrease in MRE also correlates with a decrease in pH after round 1 in BCR 1. Removal mechanisms in BCR 2 were most likely a combined precipitation of oxy‐hydroxides, carbonates, and sulfide, considering BCR 2 had much stronger evidence of sulfate reduction as discussed below.
. Lead (Pb) results for both BCR 1 and 2 were below the ORD MRL of 0.017 mg/L. It was unclear with this MRL whether the effluent met the potential water quality benchmark of 0.0043 mg/L. Sensitivity is discussed further in the data usability evaluation in Appendix B.
. Nickel (Ni) in BCR 1 effluent was fairly stable between an MRE of 50 to 70 percent for the test, with the exception of round 4 MRE that increased to greater than (>)80 percent. Ni in BCR 2 was higher than in the MIW for the first two rounds; however, as the system stabilized, concentrations decreased to 0.006 in round 5, with a post stabilization MRE range of 51 to 80 percent. The target performance criteria were generally not met in either BCR 1 or BCR 2 through the test. However, potential water quality benchmarks were achieved, with the exception of BCR 2 in the first two rounds.
. Zinc (Zn) MRE was nearly 100 percent for the first round in BCR 1, but then fluctuated between 60 and 80 percent for the remainder of the test. In BCR 2, Zn remained below 1 mg/L, with nearly 100 percent MRE for rounds 1 through 5. Performance targets were not met with BCR 1 after round 1; however, they were met in BCR 2 for the entirety of the test. Aside from round 1,
3‐5 Section 3 Evaluation Criteria, Results, and Discussion
potential water quality benchmarks were not met in BCR 1. Although BCR 2 had nearly 100 percent removal efficiency for all the rounds, the Zn levels met the potential water quality benchmark of 0.179 mg/L only for round 3. The MIW entered the system at concentrations between 60 and 70 mg/L, and toxic effects on SRBs have been observed with Zn concentrations of 20 to 25 mg/L and greater (EPA 2006). This factor may contribute a greater impact on BCR 1 with already less than ideal conditions for SRB growth as demonstrated by low VFA and sulfide output.
Other Major Metals . Aluminum (Al) MRE in BCR 1 was initially 99 percent in round one and steadily decreased as effluent concentrations increased, with a final MRE of 71 percent in round 5. Conversely, BCR 2 had an initial MRE of 69 percent, which steadily improved to 100 percent by round 5. By the end of five rounds, BCR 1 was not achieving its targeted performance goal; however, BCR 2 was well within its goal.
. Arsenic (As) was below the MRLs of 0.36 mg/L in BCR 1 and the MIW. However, As appears to be associated with the BCR 2 ChitoRem® media, as there were minor detections in the first two rounds as a result of leaching from the substrate. After the media stabilized, however, As concentrations went back down below detection.
. Calcium (Ca) in BCR 1 effluent was approximately twice as high as MIW for the entire test. In BCR 2, the Ca concentration was approximately 34 times the MIW in round 1 and decreased to approximately 7.5 times of MIW in round 5. Both substrates appeared to be sources of Ca during the test. BCR 1 appeared to be a steady source over the five rounds while BCR 2 decreased over time.
. Cobalt (Co) tracked the influent concentration fluctuations, with MRE ranging from 0.1 to 0.3 percent in BCR 1 effluent. In BCR 2, effluent was initially higher than influent as Co was leaching from the ChitoRem® substrate initially. After initial leaching, concentrations fell to below the MRL. In a similar treatability study performed by EPA (CDM Smith, 2013a), a reactor with similar substrate to BCR 1 and influent Co concentration showed a sorption trend with a subsequent saturation/desorption trend. The difference was that the effluent pH of BCR 1 is on average 1 su lower than the example study, and therefore, ad‐absorption was being inhibited by the acidity in the substrate. The EPA study also investigated a ChitoRem® reactor similar to BCR 2, and Co reacted similarly in both studies, which suggests that after an initial leaching phase, Co was removed via precipitation of oxy‐hydroxides or carbonates.
. Iron (Fe) MRE in BCR 1 was initially >90 percent in round 1 and then stabilized between 20 and 50 percent for the remainder of the test. BCR 2 had MREs of nearly 100 percent for rounds 2 through 5. Performance targets were not met with BCR 1; however, they were met with BCR 2. Removal mechanisms with Fe are a bit more complicated in barrels without pretreatment. Reactor influent had elevated DO and subsequent higher ORP, which would favor the presence of oxidized ferric Fe (Fe3+), favoring precipitation. However, the low pH of the influent MIW, pH 3 to 3.5 su, precipitation of ferric Fe would be limited, and dissolved oxidized Fe would be transported down into the reducing layers of the substrate. The transport of oxidized ferric Fe into the substrate could also be contributing to the suppression of sulfate reduction. As long as there remains a pool of oxidized Fe present, ORP will be poised above the optimal energy level for sulfate reduction (Davison 1993). Presumably, at some point vertically in the reactor, there was a transition zone where ferric Fe is reduced to ferrous and below that would be a zone that
3‐6 Section 3 Evaluation Criteria, Results, and Discussion
could foster SRB activity. This hypothesis is supported by the observation of an orange top layer on the surface of the media overlying a black layer, as described in Section 2.4.2 with the discussion on the rebuild of the ChitoRem® barrels after round 5. ORP was sufficiently low to foster reduction of ferric Fe to ferrous Fe (Fe2+); however, considering there was a lack of sulfide generation to sequester the soluble metal, very small reductions were seen in BCR 1. BCR 2 had both low ORP and elevated higher sulfide effluent, therefore, the reduced concentrations of Fe in its effluent are influenced by sequestration of ferrous Fe by sulfide and/or oxy‐hydroxide precipitation (Robinson‐Lora and Brennan 2009).
. Manganese (Mn) concentrations were elevated in the woody substrate barrels and the SAPS pretreatment barrel. Considering the SAPS did not have woody substrate in its matrix, the Mn was most likely leaching out of the compost and/or manure. BCR 1 effluent remained 0.5 to 0.25 mg/L for the entire five rounds of this test. Mn, in general, is more sensitive to reduction than Fe, meaning Mn more readily goes through reduction processes at a higher redox potential than Fe. The reverse, however, is not true, as Mn(II) is recalcitrant to oxidation and can maintain in its reduced form in oxic environments as compared to ferrous Fe which can oxidize quickly, within hours of oxygen contact (Bohm 2001). The influent Mn in BCR 1 was primarily the soluble reduced form, Mn2+, and would be expected to stay soluble in pH less than 8 (Venot et al. 2008). The legacy Mn in the manure substrate would also be solubilized by the depressed pH of the influent water while resident Mn‐oxides would have been subsequently reduced to its soluble form and contributed to the MIW. The Mn removal observed in BCR 2, with an MRE of 70 percent by round 5, was influenced by both precipitation of carbonate minerals from the dissolution of calcite and also the sorption onto the chitinous materials and the associated proteins, most likely dominated by carboxylic acids at the pH range of 5 to 8 su (Robinson‐Lora and Brennan 2010). Both Robinson‐Lora and Brennan 2010 and Venot et al. 2008 found chitin/protein mixtures to have a unique ability to sorb Mn in pH ranges that are not conducive to sorption with other SRB‐enhancing substrates.
Mercury (Round 4) . Total Mercury (THg) was at a concentration of 1.02 ng/L in BCR 1 and 14 ng/L in BCR 2. THg was reduced in BCR 1 with effluent concentrations well below the mean observed in unmined basins. The THg concentrations from BCR 2, however, increased in the effluent to concentrations above the 2.96 ng/L mean found in unmined basins across the United States. While BCR 2 effluent was below the mean concentration typically found in mined basins of 23.5 ng/L, it was well above the median concentration of 3.79 ng/L (Scudder et al. 2009). The term mined basin refers to basins with historical gold or mercury mining activity. Considering the low influent and BCR 1 effluent THg concentration, it appears that the matrix in the ChitoRem® BCR is a source for THg to the effluent.
. Methylmercury (MeHg) was below the MRL of 0.05 ng/L in BCR 1 and 1.19 ng/L in BCR2. Both the influent and the effluent of MeHg to BCR 1 was below the MRL. The MeHg from BCR 2 increased to concentrations well above the mean typically observed in both unmined and mined basins, 0.2 ng/L and 0.18 ng/L, respectively (Scudder et al. 2009).
Wet Chemistry Parameters Over the course of the test, sulfate concentrations in reactor effluent were highest in BCR 1. BCR 1 also had the highest ORP readings throughout the test, indicating that conditions optimal for sulfate reduction were not reached in the reactor. In BCR 2, sulfate was reduced by nearly an order of magnitude from round 2 through round 4, then dropped below the MRLs of 3.31 mg/L in round 5
3‐7 Section 3 Evaluation Criteria, Results, and Discussion
(Figure 3‐18 and Table 3‐5). The rapid drop in sulfate in round 5 may have been influenced by an increase in residence time within the reactors or the decrease of readily usable organics such as VFA, see below. Measurements in round 5 showed flow at BCR 2 at 0.4 L/hr, well below the target flow of 1.2 L/hr. Considering ancillary parameters, such as ORP, pH, temperature, sulfide, and VFA support the conclusion that sulfate reduction was occurring in BCR 2, it follows that extending the residence time would enhance sulfate removal.
Sulfide concentrations in BCR 1 effluent were the lowest of all reactor barrels and in fact went below reportable limits of 0.01 mg/L after round 1 (Figure 3‐19). Some sulfate reduction took place in the initial incubation period, but once the system flow was initiated, ORP conditions rose and the residual sulfide was precipitated with influent metals or flushed from the system. Elevated sulfide was observed in BCR 2 effluent over the course of the test; however, concentrations decreased over time from 8 mg/L in round 2 to 0.7 mg/L in round 5. The presence of sulfide in the effluent stream was not a direct measure of how much sulfate was being reduced in the reactor; it was only an indicator of the reaction. Sulfide can form metal precipitates and is a particularly strong ligand for reduced ferrous Fe (Davison 1993), and much of the generated sulfide can be sequestered in the media as metal‐sulfide precipitates.
Alkalinity was below the MRL of 5 mg/L as Ca carbonate (CaCO3) in the influent MIW for the entire test (Figure 3‐17). Both BCR 1 and BCR 2 had elevated alkalinity concentrations, 2,000 and 30,000 mg/L of CaCO3 respectively; however, BCR 2 had an order of magnitude higher alkalinity level than BCR 1. In both reactors, alkalinity dropped by a factor of 10 by round 5. Sulfate reduction can increase alkalinity as bicarbonate CaCO3; however, the increases in BCR 1 appear to be related to dissolution from limestone since there was no apparent evidence of sulfate‐reducing activity. Although there was evidence of sulfate reduction in BCR 2, the steady decrease in alkalinity over time suggests that the dissolution of calcite from the crab shells in the ChitoRem® substrate was the significant contributor to alkalinity in this system.
VFAs in BCR 1 were below the MRLs, with a small accumulation in round 1 as a carryover from the incubation period (Figure 3‐20). BCR 2 had concentrations over 13,000 mg/L of acetic acid, which decreased to 2,000 mg/L by the end of the test in round 5. Although the presence of acetic acid in BCR 2 throughout the test indicated activity of chitin fermentation and subsequent SRB activity, the steady decrease was indicative of a gradual slowdown in biological activity. ChitoRem® consistently released higher concentrations of organics for SRB to use compared to the woody substrate.
Summary In general, the differences in performance between non‐pretreatment woody substrate and ChitoRem® reactors were quite stark. The full potential of the ChitoRem® reactors was difficult to gauge with the current 2013 results considering that design flow was not achieved for the five rounds of the test. The treatability study was also terminated early as a result of an unforeseen reduction in flow at the adit portal that eliminated the feed water to the system.
BCR 1 did not achieve conditions that were conducive for sulfate reduction and overall had the poorest MRE out of all six reactor systems. BCR 1 did not achieve target MRE values with Fe and Cr, similar to BCR 3 described below, and was the only reactor that did not achieve 90 percent MRE with Zn. Compared to the other two woody substrate BCRs, 3 and 5, that had pretreatment, it was clear that untreated MIW adversely affected BCR 1. BCR 2 had fairly good results in MRE of target and other major metals, with the exception of Mn and Ni, and was much less severely impacted by untreated
3‐8 Section 3 Evaluation Criteria, Results, and Discussion
MIW. BCR 2 was the only reactor to not achieve target MRE values with Al. Co, Mn, and Ni are metals included in this discussion that failed to be removed to the 90 percent target in all six reactor systems.
The pool of Hg associated with the ChitoRem® matrix (both ChitoRem® and sand) that appears to have been contributed to the treated MIW effluent could be either in an inorganic Hg(II) form or the methylated MeHg form. ChitoRem® is composed of material sourced from aquatic organisms, and MeHg is the form of the toxic metal that most commonly accumulates in living tissue. The BCRs also are designed to enhance the activity of sulfate‐reducing bacteria, one of the primary microorganisms that is responsible for the conversion of Hg(II) to MeHg. Without further studies, it is unclear whether or not the increase of MeHg observed in BCR 2 was a result of methylation of matrix resident Hg(II) by the internal sulfate reduction activity or the release of pre‐methylated MeHg from the matrix. By round 5, the flow in BCR 2 was 0.4 L/hr, 30 percent of design flow, and flow rate may have an influence on the magnitude of the Hg release.
The higher release of readily usable organics by BCR 2 and the longer residence time in BCR 2 facilitated the establishment of sulfate‐reducing conditions and metal removal compared to BCR 1. 3.2.3 SAPS Pretreatment with BCR 3 and 4 The purpose of the installation of BCR 3 (woody substrate) and BCR 4 (ChitoRem®) was to compare the performance of the two substrates in both the ability to increase pH and induce a greater than 90 percent MRE with the incorporation of SAPS pretreatment. SAPS are systems that use limestone to increase pH and a 50/50 mixture of compost and manure, which provides carbon and bacteria, as well as other important system needs. Earlier bench scale tests in previous EPA studies (CDM Smith, 2013a) concluded that elevating MIW as a pretreatment, using NaOH, was not improve efficiency of BCRs. However, this study investigated the effect of elevating pH and decreasing influent DO as a pretreatment in a real world application. Table 3‐2 and Figures 3‐1 to 3‐21 present the results.
Field Parameters Field parameters are presented in Table 3‐3 and Figures 3‐1 to 3‐6.
The pH in the SAPS pretreatment barrel dropped from 6.2 su in round 1 to 5.8 su in round 2 and remained steady until round 5 when it came back up to 6 su. In a previous study performed by EPA (CDM Smith, 2013a), a similar SAPS reactor elevated MIW influent from a pH ~3 to 6.8 to 7 su. Although the size and substrate composition of this study was the same as the EPA study, the flow in the current study was initially 4 times higher, and then after round 3, 2 times higher than the previous study, which may account for the lower pH values attained in the SAPS effluent presented in this document. The SAPS effluent water quality was subsequently the BCR 3 and BCR 4 influent water quality, and therefore the SAPS pretreatment was successful in elevating the pH prior to BCR input. The pH in BCR 3 did not increase much from SAPS effluent, increasing 0.1 to 0.3 su over the course of the test from the influent value. BCR 4 pH increased 0.5 units from inflow though the test to round 5, with the exception of round 2 where pH increased 1.2 su from its influent pH. Generally, the pH in the SAPS pretreatment systems were fairly stable and within the range of SRB growth (EPA 2006).
Conductivity in the SAPS did not change much from the MIW, staying within 200 to 300 µS/cm for the length of the test. In BCR 3, conductivity was slightly elevated after the 2‐week stagnant incubation in round 1 but then decreased to within a range comparable to the MIW and the SAPS effluent. The conductivity in BCR 4, however, was initially 24,000 µS/cm after the 2‐week incubation period. BCR 4’s trend was similar to that of BCR 2, with a reduction in magnitude. The higher conductivity
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correlates with the general trend of increased alkalinity, anions, Mn, and sodium observed with the ChitoRem® media similar to observations in a previous EPA study (CDM Smith, 2013a).
The temperature of the SAPS pretreatment was initially several degrees higher than the BCRs in round 1. This was most likely due to the orientation of the pretreatment barrels and where the sun falls on the site and the fact that the system had been sitting stagnant for a 2‐week period and flow had just been initiated 40 hours prior to round 1 sampling. Similarly, the ChitoRem® pretreatment barrel had elevated temperature in the first round. As the sun comes over the trees at the site, the rays hit the pretreatment barrels first, an hour or two prior to hitting the BCRs, which may account for the elevated temperature in the first round. Figure 2‐4 shows the pretreatment barrels in the sun, and the BCRs are shaded. As the flow continued after round 1, the influent water acted as a temperature buffer, bringing the temperature down in the pretreatment barrels closer to that of the BCRs.
Initial redox conditions induced by the SAPS pretreatment barrel were below an ORP of ‐100 mV for the first two rounds, after which the ORP increased linearly to +25 mV, following a similar trend to BCR 1 towards the end of the test. ORP in BCR 3 showed increases in redox condition relative to inflow. There are several factors that may account for this observation. First, the redox conditions of the influent may be higher as the flow enters the BCR than when it exits the SAPS pretreatment (where it is measured). There are several points in the line connecting the SAPS and the BCRs that introduce oxygen into the flow. The first was at the SAPS drainage manifold, which had an anti‐syphon valve that opens the flow to the atmosphere. The second was in the headspace of the BCR, which was vented to the atmosphere. These two factors could be elevating the ORP to a value higher than that being measured in the SAPS pretreatment barrel effluent. BCR 3 redox conditions dropped to below ‐200 after round 3, which correspond to a system‐wide reduction in flow and measures to prevent BCR 3 from receiving extra flow during BCR 4 run times (described in section 2.4.2). The results demonstrated that SAPS pretreatment enhanced reducing conditions in BCR 3 to a level more optimal for SRB as compared to its non‐pretreatment counterpart BCR 1. Redox conditions in BCR 4 were very similar to its non‐pretreated counterpart BCR 2, with the exception that BCR 4 remained below ‐200 mV in round 5 when BCR 2 increased slightly above ‐200 mV. It appears that with the current configuration, redox conditions optimal for SRB growth in BCR 4 were not markedly enhanced by SAPS pretreatment.
Metals Observations of MRE ranges (Table 3‐4), and comparison to screening benchmarks (Table 3‐1) are as follows.
Target Metals . Cadmium (Cd) was removed from the SAPS effluent from a range of 70 to 98 percent although its performance after round 1 was the poorest of all treatment barrels. BCR 3 effluent was below the MRL of 0.002 mg/L for the entire test as was BCR 4, with the exception of a small detection in round 1. Both pretreated BCRs were able to meet their 90 percent reduction target. Considering that the MRL was higher than the potential water quality benchmark, it was inconclusive as to whether or not Cd was removed to a level below the benchmark. The SAPS pretreatment improved BCR 3’s and BCR 4’s ability to remove Cd as compared to the non‐ pretreatment counterparts BCRs 1 and 2.
. Chromium (Cr) removal in the SAPS pretreatment followed a similar trend to BCR 1, with concentrations in the effluent just slightly higher than the non‐pretreatment BCR, ranging from 10 to 60 percent removal. BCR 3 also followed a similar trend, increasing concentration in
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rounds 2 and 3 then decreasing in rounds 4 and 5, ranging from 60 percent to over 90 percent over the duration of the test. BCR 4 brought Cr concentrations down to, or below, the MRL of 0.024 mg/L over the course of the test, with MRE greater than 88 percent. It was likely that efficiencies would have been observed over the target 90 percent if the MRL had been lower, as improved performance in round 1 was observed over the untreated ChitoRem® reactor BCR 2. Both BCRs 3 and 4 were able to maintain effluent below the potential water quality benchmark of 0.111 mg/L for the entire test. While both SAPS pretreated and non‐pretreated ChitoRem® reactors were able to maintain effluent below the MRLs and potential water quality benchmark for Cr, the SAPS pretreatment aided the woody substrate in achieving potential water quality benchmark.
. Copper (Cu) concentrations in SAPS pretreatment effluent followed a similar in trend with a higher magnitude as compared to BCR 1 results, stabilizing near 0.2 mg/L from event 2 through 5. Even though the SAPS had the highest effluent concentrations out of all other reactor barrels, it still achieved an MRE of 90 to 98 percent. BCR 3 effluent increased in the first three rounds and then dropped in the last two, with values below the MRL of 0.007 mg/L in round 5. MRE for BCR 3 were 97 percent to near 100 percent for the entire test. BCR 4 had low but detectable levels of Cu in its effluent for the first two rounds but then dropped below detection for the last three rounds. Both BCRs 3 and 4 were able to meet their target removal goals and had discharge levels that met the potential water quality benchmark of 0.012 mg/L by round 5. Similar removal mechanisms observed in BCR 1 (removal via oxy‐hydroxide and carbonate precipitation) are most likely occurring in BCR 3, and considering the drop in ORP and sulfate in the last two rounds, it was likely that precipitation via sulfide sequestration was occurring as well. Removal mechanisms operating in BCR 4 are similar to those occurring and discussed with BCR 2. Sorption was most likely playing a more significant role in both BCRs 3 and 4 considering the influent metals concentrations were considerably lowered and were occupying reactive sites at a much lower rate.
. Lead (Pb) concentrations in BCRs 3 and 4 effluents are all below the MRL of 0.017 mg/L. It was unclear with an MRL of 0.017 mg/L whether the effluent met the potential water quality benchmark of 0.0043 mg/L. Sensitivity is discussed further in the data usability evaluation in Appendix B.
. Nickel (Ni) was initially lowered in SAPS pretreatment in round 1, and then rebounded to concentrations just under the influent for rounds 2 and 3. In rounds 4 and 5, concentrations rose higher than influent concentrations. This pattern was consistent with an adsorption removal mechanism with a subsequent saturation and breakthrough. Ni in BCR 3 dropped to below the MRL of 0.004 mg/L in round 2 and remained at these levels through the rest of the test. Ni was elevated in the effluent compared to its influent and the original MIW, indicating Ni was leaching from the ChitoRem® material, similar to BCR 2. A near linear reduction occurred in BCR 4 from onset of the test to round 4 where levels remained at or near the MRL. The MIW was below the potential water quality benchmark of 0.079 mg/L, and the only exceedances were from BCR 4 in round 1 when Ni leached from the ChitoRem® substrate. The improved performance in BCR 3 compared to BCR 1 was not from a decreased influent concentration, considering there was very little reduction, and in some cases, increased as observed in the SAPS pretreatment. Most likely, the improved performance was linked to elevated pH in the influent, which would increase the likelihood of pH sensitive Ni/oxy‐hydroxide formation and sorption. Good Ni removal occurred prior sulfide generation; metal sulfide precipitation did not
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dominate early on. After the initial leaching, similar mechanisms to BCR 2 were most likely dominating in BCR 4.
. Zinc (Zn) in the SAPS pretreatment effluent after the first round had small MREs between 10 and 30 percent. The MRE for BCR 3 was greater than 98 percent for the whole test and greater than 96 percent for BCR 4. Both BCR 3 and BCR 4 were above the potential water quality benchmark of 0.179 mg/L by the end of the 2‐month test. Zn removal was improved in the pretreated BCR 3 over the non‐pretreated BCR 1. This, similar to Ni, was more the result of pH elevation than metal concentration reduction, considering the SAPS have poor Zn removal. Zn concentrations in BCR 4 suggest that adsorption and subsequent breakthrough was occurring even though concentrations at the end of round 5 were still less than 90 percent of the influent MIW.
Other Major Metals . Aluminum (Al) removal in the SAPS pretreatment tracked with the performance of BCR 1 and maintained a MRE above 95 percent for the test. BCR 3 appeared to have Al associated with leachate from its substrate in the initial round 1, increasing the concentration from the SAPS pretreatment slightly. After round 1, BCR 3 decreased below the SAPS and continued to decrease, falling below MRLs of 0.095 mg/L at round 5. BCR 4 effluent increased from the SAPS pretreatment with an overall MRE of 50 percent and followed the trend observed in BCR 2. The target 90 percent MRE was accomplished in both BCRs 3 and 4. The initial increase in BCR 3 can be explained by leaching from the substrate; however, that explanation was not applicable to BCR 4. The non‐pretreated BCR 2 reactor reduced Al in MIW throughout the test while BCR 4 added Al to the water it received from the SAPS. The behavior of the ChitoRem® reactors in this test was indicative of media that were semi‐saturated with Al and sensitive to concentration gradient shifts. In this scenario, it appears that higher concentrations drove Al onto sorption sites while lower concentrations drove Al from the media into solution. The gradual decrease in Al concentration with time in all of the ChitoRem® reactors would then be attributed to the sequestration of Al from the precipitation of oxy‐hydroxides and sulfides (Robinson‐Lora and Brennan 2009) where precipitation mechanisms eventually take over and the system was no longer governed by sorption. The steep drop at the end coincides with a marked decrease in system flow in the ChitoRem® reactors where reaction time was increased up to 4 times that of the design.
. Arsenic (As) was not detected in the SAPS pretreatment, BCR 3, or MIW. As with BCR 2, BCR 4 ChitoRem® substrate leached As for a short time at the onset of the test, dropping below the MRL after 1 month. This was observed in a similar study conducted by the EPA (CDM Smith, 2013a).
. Calcium (Ca) in SAPS pretreatment effluent was approximately twice the concentration as the MIW for the entire test, nearly identical to BCR 1. BCR 3 added similar contributions to that of the SAPS, with concentrations nearly triple that of the MIW. BCR 4 initially had concentrations of Ca more than 20 times higher than MIW and dropped slowly over time in a similar pattern to the other ChitoRem® reactors. Both woody substrate and ChitoRem® are sources of Ca.
. Cobalt (Co) concentrations were nearly identical after round 1 between SAPS pretreatment and MIW. After stabilization in the first two rounds, BCRs 3 and 4 dropped below the MRL. Considering that the MRL was less than 50 percent below MIW, it was not possible to determine the removal efficiency.
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. Iron (Fe) removal in the SAPS pretreatment was poor over the course of the test, with MREs of 10 to 30 percent after the first round, very similar to BCR 1. BCR 3 showed improved removal over its non‐pretreated counterpart, with MREs ranging from 50 to 76 percent. BCR 4 MREs ranged from 94 percent to near 100 percent; however, it did not perform as well as its non‐ pretreatment counterpart BCR 2. BCR 3 showed improved Fe removal with SAPS pretreatment, following a similar concentration trend over time as BCR 1. MREs dropped from 50 percent in rounds 2 and 3 to 75 percent in rounds 4 and 5. The correspondence with both a drop in flow to increase residence time and a drop in redox condition to a level more conducive to sulfide production was indicative of enhanced removal by precipitation. BCR 4 achieved nearly 100 percent Fe removal toward the end of the test; however, it did not achieve concentration as low as BCR 2. Although the difference between the two was small in comparison to the influent, it may be attributed to sequestration in the oxidized surface of BCR 1 substrate.
. Manganese (Mn), as discussed above, was associated with the compost and manure in this treatability test. The SAPS pretreatment and BCR 3 were both elevated from MIW similar to BCR 1. BCR 4 initially showed some potential to remove Mn at more than 50 percent in round 2; however, MRE decreased over the next three rounds, and BCR 4 did not perform as well as its non‐pretreated counterpart BCR 2. The pattern with the reduced performance with Mn removal in BCR 4 relative to BCR 2 was nearly identical to that observed with Fe. Transport of these two metals was strictly controlled by redox conditions and speciation. One major difference between BCR 2 and BCR 4 was that BCR 2 has high redox conditions at the influent, and oxidized metal species may be more likely to get sequestered there even under acidic conditions. In BCR 2, as water travels down through the substrate, pH conditions are increasing while redox conditions are decreasing. Although this was not investigated, the hypothesis was that pH increases faster than redox decreases moving down the substrate. This would create a zone that could favor oxidized substrate precipitation.
Mercury (Round 4) . Total Mercury (THg) was reported at a concentration of 0.65 ng/L and 22 ng/L in BCR 3 and 4, respectively. THg in BCR 3 was reduced to 0.65 ng/L, whereas concentrations were increased to 22 ng/L in BCR 4. The removal observed in BCR 3 relative to BCR 1 may have been due to mercury removal in the SAPs pretreatment barrel, resulting in a reduced mercury load in BCR 3 influent. However, it appears that the SAPS pretreatment and BCR 4 together resulted in higher THg in the effluent relative to either BCR 2, as BCR 4 effluent was nearly double that of the non‐ pretreatment BCR.
. Methylmercury (MeHg) was reported at a concentration of 0.09 ng/L and 1.64 ng/L in BCR 3 and 4, respectively. The increase in BCR 3 to above the MRL of 0.05 is most likely due to the increased sulfate reduction activity relative to BCR 1, resulting in a fraction of the Hg(II) passing through the system becoming methylated. The effluent concentration of MeHg in BCR 1 is still below the concentrations typically found in mined and unmined basins around the United States. The MeHg in BCR 4 effluent was more elevated than in BCR 2 effluent, but the increase was not as large as the observed increase in THg between the two barrels.
Wet Chemistry Parameters The SAPS pretreatment reduced sulfate by more than 50 percent over the length of the test (Figure 3‐ 18 and Table 3‐5). ORP readings in the SAPS, not as high but similar to BCR 1, suggest that sulfate reduction was not occurring. BCR 3 showed a 75 percent decrease in sulfate from MIW and had ORP values towards the last two rounds of the test that were conducive to sulfate reduction. BCR 4
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observed a reduction of more than 90 through a majority of the test, however, after an initial drop, steadily increased in concentration from round 2 to 5. BCR 4 was the only ChitoRem® reactor that did not dramatically decrease from round 4 to round 5 when all ChitoRem® reactors’ flow decreased.
Sulfide was not evaluated in SAPS effluent (Figure 3‐19). Sulfide generation was observed in BCR 3 and BCR 4, which indicate the activity of SRB throughout the course of the test. Sulfide concentration decreased in BCR 3 from rounds 2 to 4, then increased slightly in round 5. In BCR 4, sulfide fluctuated between 2 and 6 mg/L until round 5 when it increased to 200 mg/L. Although BCR 4 did not drop in sulfate like the other ChitoRem® reactors in round 5, the quantity of sulfate removed from the MIW in BCR 4 was more than enough to account for the peak in sulfide observed in round 5.
Alkalinity in BCR 3 was elevated as compared to BCR 1 (Figure 3‐17), initially at 5000 mg/L CaCO3 after incubation and then decreasing to 200 mg/L by the end of the test. BCR 4 was initially increased to 20,000 mg/L as CaCO3, decreasing over the five rounds to nearly a factor of 10 less at 3,000 mg/L as CaCO3. BCR 4 appeared to be elevated in alkalinity as a result of SAPS pretreatment, which was aided by the contribution of limestone in the pretreatment barrel. BCR 4 was elevated compared to BCR 3, and followed a near identical trend to BCR 2. However, BCR 4 was consistently 20 to 40 percent lower in alkalinity than its non‐pretreatment counterpart. Based on the increases observed in BCR 3 compared BCR 1, the SAPS pretreatment was adding a small amount of alkalinity to the BCR influent, 0 to 1,500 mg/L as CaCO3 over the course of the test. The SAPS was also increasing the pH, which appears to be inducing less calcite dissolution in BCR 4 as compared to BCR 2, resulting in slightly lower alkalinity in the effluent.
Acetic acid generation was observed in BCR 3 and 4 (Figure 3‐20). BCR 3 had values elevated above 1,000 mg/L and gradually decreased over the test down to less than 5 mg/L at the end of the test following a similar trend to BCR 1. BCR 4 had elevated acetic acid generation initially at 8,000 mg/L, decreasing incrementally through the test to a final 2,000 mg/L, similar to the trend of BCR 2 with a 20 to 50 percent reduction in magnitude. The decreasing trend observed in BCR 3 indicate that production of VFA breakdown products was either slowing down or that SRB and other anaerobic organisms were consuming as an electron donor (Robinson‐Lora and Brennan 2009). Considering that ORP drops to a level more conducive to SRB in the last two rounds and presence of sulfide concentrations in the effluent spike, it was likely that this was evidence of increased SRB activity. However, based on the trends, it appears SRB activity was decreasing through the test. Higher concentrations of VFA are typical with the ChitoRem® material as high surface area of organics contributes to a greater quantity of breakdown products. BCR 3 showed steady sulfate decreases over the course of the test and a large sulfide peak in round 5, indicating that SRB growth was active and increasing at the end of the test.
Summary In general, BCR 4 performed better than BCR 3 in removing metals from MIW with SAPS pretreatment. Considering the study was prematurely stopped after 2 months, it is difficult to project how the barrels would perform further out in the future if the adit water had continued to flow. However, there are some indications that BCR 3 was improving performance of SRB in the last round of sampling.
Over all, BCR performance was improved with SAPS pretreatment. BCR 3 removed more Fe than BCR 1 although 90 percent removal was not achieved. BCR 4 performance in MRE was very similar to BCR 2, as it was able to remove the same target and other major metals to the 90 percent goal. BCR 4 had poorer performance removing Mn than BCR 2 (BCR 2 did not reach 90 percent removal either),
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despite pretreatment. BCR 4 at the end also was less effective in removing Fe than BCR 2 although both were able to meet the 90 percent requirements. It appears that in redox sensitive compounds, the benefit present in the un‐pretreated BCR 2s oxic‐anoxic interface within the primary treatment media was providing a greater removal benefit than having a separated pretreatment reactor although the differences were small. Ultimately, SAPS pretreatment improved the performance of woody substrate although the problems BCR 1 encountered removing Fe and Cu were not resolved with BCR 3. Performance of BCR 4 in most cases was very similar to BCR 2, with a few cases of poorer performance (Mn and Fe).
Similar to BCR 2, the ChitoRem® matrix in BCR 4 appears to be a source of THg and MeHg in BCR effluent. The SAPS pretreated ChitoRem® BCR had twice the concentration of THg in its effluent as compared to the non‐pretreated BCR 2. It is unlikely that the SAPS was a source of mercury considering its matrix was composed of the same material used to construct BCR 1, 3, and 5. The SAPS pretreatment buffered the influent to BCR 4, with a pH near 6 su in round 4, suggesting that the leaching of THg from the ChitoRem® media in BCR 2 was not related to lower pH in the influent. While the change in water condition by the SAPS may have influenced the magnitude of the Hg release, flow also may have played a factor. In round 5, BCR 4 was flowing at a rate of 0.7 L/hr, 60 percent of the design flow rate. BCR 4 had the highest flow rate of the ChitoRem® BCRs corresponding with the highest THg in its effluent. 3.2.4 ChitoRem® Pretreatment with BCR Barrels 5 and 6 The purpose of the installation of BCR 5 (woody substrate) and BCR 6 (ChitoRem®) with a ChitoRem® pretreatment was to compare the performance of the two substrates, as well as compare them to their non‐pretreated counterparts BCR 1 and 2, and their SAPS pretreatment counterparts BCR 3 and BCR 4. The ChitoRem® pretreatment reactor consists of an identical composition as BCRs 2, 4, and 6. The one big difference between these pretreatment reactors and the BCRs was how the system was designed; twice the amount of flow was passed through the pretreatments as compared to the flow passed through the BCRs. Table 3‐2 and Figures 3‐1 to 3‐21 present the results.
Field Parameters Field parameters are presented in Table 3‐3 and Figures 3‐1 to 3‐6.
The ChitoRem® pretreatment initially increased to above a pH of 7 su in round 1 after the initial incubation period. The pH dropped to 5.9 su, approximately 0.5 su below BCR 2 in round 2, due to flow issues. The issues with ChitoRem® flow were temporarily solved after round 2 although the media began to back up and decrease flow in rounds 4 and 5. ChitoRem® pretreatment pH then increased at the end, with a final pH of 6.3 in round 5. BCR 5 had an initial pH of 6.5, dropping to 6.3 su corresponding to the ChitoRem® pretreatment drop. BCR 5 in the latter portion of the test remained approximately 0.3 to 0.4 su above the ChitoRem® pretreatment effluent. BCR 6, after round 1, maintained a stable pH between 6.3 and 6.4 su for the remainder of the test. The influence of flow in the ChitoRem® pretreatment was apparent for the test, with higher pH readings in periods of lower flow. BCR 5 appeared to be more sensitive to the pH of the pretreated water than was BCR 6.
Conductivity in the ChitoRem® pretreatment increased the least out of all ChitoRem® reactors. Initial conductivity readings in the pretreatment rose to initial values of 7,000 µS/cm and then dropped down to below 3,000 µS/cm for the remainder of the test. BCR 5 contributed to the pretreatment conductivity, more than doubling its conductivity to 15,000 µS/cm and then also decreased to 3,000 µS/cm for the remainder of the test. BCR 6’s magnitude and pattern of conductivity were similar to BCR 2. Conductivity was similar among like substrates, as woody substrate barrels observed similar
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conductivities, and ChitoRem® barrels observed similar conductivities. BCR 5 conductivity was controlled by the conductivity of the pretreatment after the early rounds.
The temperature regime in all BCRs and pretreatment barrels follows similar magnitude and patterns, with pretreatment barrels slightly elevated in the early rounds, and then temperatures became nearly homogenous in all reactors in the later rounds.
Redox conditions in all the ChitoRem® pretreatment barrels and in both BCRs 5 and 6 were nearly identical, with the exception of an increased ORP in the pretreatment in round 4. Redox conditions fluctuated between ‐200 and ‐300 mV after round 1. BCRs 5 and 6 after round 1 had redox conditions that were the most optimal for SRB activity out of all of the BCRs in this test.
Metals Observations of MRE ranges (Table 3‐4), and comparison to screening benchmarks (Table 3‐1) are as follows.
Target Metals . Cadmium (Cd) was reduced to below the MRL of 0.002 mg/L, after round 1 in ChitoRem® pretreatment and BCRs 5 and 6, with MREs near 100 percent for both reactor systems. Considering the potential water quality benchmark for Cd, 0.00035 mg/L, was below the MRL, it was inconclusive as to whether discharge benchmark were met. ChitoRem® pre‐treatment contributed to most of the overall Cd removal.
. Chromium (Cr) removal was near 100 percent for the first two rounds and then fell to 70 percent in round 3. By round 5, the removal in the pretreatment had returned to near 100 percent. After round 1, MRE in BCRs 5 and 6 was near 100 percent, and the values were below the MRL of 0.024 mg/L for the remainder of the test. All reactors maintained discharge values below the potential water quality benchmark of 0.111 mg/L. A decrease in Cr removal in the ChitoRem® pretreatment barrel corresponds with system maintenance to seal the vent in the pretreatment barrel lids. Prior to this, it was observed that the pretreatment barrels were not receiving full design flow prior to round 3. Observations confirm that all of the design flow passed through the ChitoRem® barrel in round 3, after the lids were sealed. After round 3, the flow began to back up to the head tanks in the ChitoRem® pretreatment, and therefore flow was once again less than design flow through the barrel in rounds 4 and 5. Lower flows would equate to longer reaction times and therefore contribute to increased MREs in most cases. ChitoRem® pretreatment clearly improved BCR 5’s MRE performance with Cr as compared to BCRs 1 and 3. It appears that the pretreatment also improved BCR 6’s performance, as it decreased to below the MRL earlier than both BCR 2 and BCR 4. ChitoRem® pre‐treatment contributed to most of the overall Cr removal.
. Copper (Cu) removal in the ChitoRem® pretreatment and BCRs 5 and 6 was virtually identical as Cr discussed above. After the initial round, both systems were able to maintain effluent below the potential water quality benchmark of 0.012 mg/L. ChitoRem® pretreatment clearly improved BCR 5’s MRE performance with Cu as compared to BCRs 1 and 3. It appears that the pretreatment also improved BCR 6’s performance, as it decreased to below the MRL earlier than both BCR 2 and BCR 4. ChitoRem® pre‐treatment contributed to most of the overall Cu removal.
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. Lead (Pb) concentrations in BCRs 5 and 6 were all below the MRL of 0.017 mg/L. It is unclear with the ORD MRL on 0.017 mg/L if the 0.0043 mg/L potential water quality benchmark were met.
. Nickel (Ni) in the ChitoRem® pretreatment was reduced to below the MRL after round 1. BCR 5 also decreased Ni concentrations down to at or near the MRL after round 1. BCR 6 initially increased Ni concentrations in the flow it received from the pretreatment initially to values greater than MIW and then continued to add Ni to a lesser extend with fairly stabilized concentrations of 0.01 to 0.02 mg/L for the remainder of the test. The ChitoRem® pretreatment behaved differently than BCR 2 although both have identical substrate compositions. The one difference between the two barrels was that twice the flow passed through the pretreatment barrels as compared to the flow passing through each BCR. Considering it appears equilibrium sorption/desorption reactions were influencing a media that appeared to have a resident reservoir of Ni, it appears that an increase in flow enhanced the media’s ability to sequester more Ni than in the BCRs. BCR 5 had a mild Ni contribution after the incubation period and then dropped down to the MRL from round 2 to round 5, in a similar fashion to BCR 3. BCRs 6 and 4 both have similar inputs and are nearly identical in their behavior, indicating that the same mechanisms occurring in BCR 6 are those described with BCR 4. There did not appear to be an observable benefit to Ni MRE with the incorporation of the ChitoRem® pretreatment in either BCR 5 or BCR 6.
. Zinc (Zn) was reduced by the ChitoRem® pretreatment by nearly 100 percent for the entire test. MRE for both BCR 5 and 6 were nearly 100 percent as well. It appears that a small amount of breakthrough occurred in all three reactors after round 3, bringing their effluent slightly above the potential water quality benchmark of 0.79 mg/L. ChitoRem® pre‐treatment contributed to most of the overall Zn removal when considering Zn effluent in BCR 5 and BCR 6 compared to adit water.
Other Major Metals . Aluminum (Al) removal through the ChitoRem® pretreatment was 97 percent and greater, improving over time and dropping below the MRL by round 5. BCR 5 had a similar trend and magnitude to that of the pretreatment through the test. Al was added to the flow through in BCR 6 and remained elevated from the pretreatment until round 5 when both dropped below the MRL. The ChitoRem® pretreatment had the same substrate composition as BCR 2; however, the ChitoRem® pretreatment reduced Al by 97 percent initially while BCR 2 had an MRE of 69 percent. The only difference between the two was that the pretreatment reactors received twice as much flow as the BCRs. This phenomenon of greater metals sequestration with higher flow was also observed with the Ni comparison between these two barrels described above. The drop to undetected at the MRL in round 5 for the ChitoRem® barrels was most likely due to the increased residence time induced by the flow slow down.
. Arsenic (As) was below the MRL, 0.036 mg/L, for the ChitoRem® pretreatment for the entirety of the test. BCR 5 was below detection after round 1 for the rest of the test as well. Similar to other ChitoRem® barrels, As leached from the media in BCR 6 initially and then stabilized down to, or just above, the MRL through round 5.
. Calcium (Ca) concentrations were increased in the ChitoRem® pretreatment reactors to nearly 10 times that of the MIW influent to roughly 9,000 mg/L, decreasing over the course of the test to 200 mg/L at round 5. BCR increased the Ca a similar magnitude as the other woody substrate
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reactors by approximately 100 mg/L over the test. BCR 6 increased Ca by a similar magnitude and followed the same trend as BCR 2. Both BCR substrates are sources of Ca to the system effluent; however, the ChitoRem® had an order of magnitude higher contribution to that of the woody substrate, reflective of the high quantity of Ca carbonates associated with the chitin and large surface area (Robinson‐Lora and Brennan, 2013).
. Cobalt (Co) was increased in all reactors in the first round and then dropped below the MRL. Considering that the MRL for Co was 10 to 20 percent below MIW, it was unclear if the reactors were able to reach 90 percent removal.
. Iron (Fe) was reduced in ChitoRem® pretreatment effluent to near 100 percent for the first two rounds, with performance decreasing from round 3 to 5, ranging from 50 to 90 percent removal. BCR 5 had the best Fe removal compared to the other 5 BCR systems, dropping to below the MRLs of 0.105 mg/L after round 1, with a slight increase to 0.2 mg/L in the last round. BCR 6 initially had an MRE of 90 percent in round 1, 10.5 mg/L, but improved to near 100 percent from round 3 to round 5. The decrease in performance with the ChitoRem® pretreatment corresponds to a maintenance procedure to seal the lid and force all of the design flow through the reactor. A decrease in removal efficiency can be seen in Cr, Cu, and Mn as well. The ChitoRem® pretreatment increased the performance of BCR 5, as BCR 1 (non‐ pretreatment) and BCR 3 (SAPS pretreatment) essentially had the poorest performance. The removal mechanism that was enhanced with BCR 5 was reduced ferrous Fe scavenged via sulfide precipitation, as BCR 5 had evidence of the highest sulfide production over most of the test, see below. BCR 6, although not quite as efficient in Fe removal as BCR 5, achieved near 100 percent removal in the last three rounds of the test. Its performance was very similar in magnitude and pattern to that of BCR 2, non‐treatment, and better than BCR 4 (SAPS pretreatment).
. Manganese (Mn) removal in the ChitoRem® pretreatment reactor started at 80 percent and then appeared to have little or no treatment effect in the last three rounds. BCR 5 increased Mn in its effluent for rounds 1 and 2 and then maintained roughly a 25 percent removal for the last three rounds. BCR 6 was a source as well for the first two rounds and then maintained MREs ranging from 60 to 70 percent in rounds 3 through 5. There was a source of Mn in both woody substrate and ChitoRem® reactors. Leaching of Mn from the substrates was enhanced when influent concentrations are decreased, inducing a concentration gradient from solid phase to liquid phase. Effective Mn removal had been demonstrated in an EPA study (EPA 2006) under both anaerobic and aerobic conditions with increased protein, similar to ChitoRem®. The study also noted that Mn had the lowest removal efficiency of other tested metals due to the stability of Mn2+. Results could have been further impacted by the generation of MnSO4(aq), which at high sulfate concentrations (1,000 mg/L) can account for up to 27 percent of the Mn species; the aqueous complex would prevent Mn sorption and decrease its removal efficiency (Robinson‐Lora and Brennan 2009). Sulfate influent in this study was near 2,000 mg/L which suggests that ¼ of the Mn could have been bound up as MnSO4. A number of other studies have also observed poor MRE with Mn under anaerobic conditions (Benner et al. 1999; EPA 2006; and Venot et al. 2008). The observed complex nature of Mn removal in multiple studies and the fact that no treatment system in the current study removed Mn to the target 90 percent implies a need for further study in order to design a system to effectively remove it from MIW.
3‐18 Section 3 Evaluation Criteria, Results, and Discussion
Mercury (Round 4) . Total Mercury (THg) was reported at a concentration of 8.9 ng/L and 12 ng/L in BCR 5 and 6, respectively. THg increased to 9.8 ng/L in BCR 5, well above the mean typically found in unmined basins. Although BCR 6 effluent was elevated 12 ng/L from the adit MIW, it was not elevated as much as either BCR 2 or BCR 4.
. Methylmercury (MeHg) was reported at a concentration of 1.19 ng/L and 2.7 ng/L in BCR 5 and 6, respectively. As with THg, BCR 5 is possibly elevated in MeHg due to an increase in the BCR influent from the ChitoRem® pretreatment. Whereas THg in BCR 6 effluent is the lowest of the ChitoRem® BCRs, its MeHg concentration was the most elevated and higher than what is typically found in unmined and mined basins in the United States, 0.2 and 0.18 ng/L, respectively.
Wet Chemistry The ChitoRem® pretreatment reactor decreased sulfate levels to 500 to 700 mg/L for rounds 1 through 3 after which concentrations dropped to 50 mg/L in round 5 (Figure 3‐18 and Table 3‐5). Sulfate concentrations in BCR 5 were fairly stable from rounds 1 through 3 at 300 mg/L and then dropped in rounds 4 and 5 to near 50 mg/L. BCR 6 had the best performing sulfate removal, maintaining concentrations of 60 mg/L from rounds 2 through 3 and then dropping in rounds 4 and 5 to 4 mg/L. The drop in round 5 in the pretreatment reactor corresponds to observation that the flow had dropped to less than half of the design flow, and increased residence time most likely played a large factor in the concentration drop. The magnitude of the decrease in BCRs 5 and 6 after round 3 corresponds to the drop observed in the ChitoRem® pretreatment, and therefore the reduction toward the end in both these systems was controlled by the pretreatment.
Sulfide was not evaluated in the pretreatment barrels (Figure 3‐19). BCR 5 ranged from 10 to 60 mg/L from round 2 through round 4 and then increased to just over 100 mg/L in round 5, which could be indicative of an internal change to sulfate‐reduction. BCR 6 maintained a sulfide concentration of near 10 mg/L for a majority of the test, with the exception of round 4 when concentrations dropped temporarily to 5 mg/L. Both BCR 5 and 6 had ORP levels at or near the range for optimal SRB activity. With the observed reduction in sulfate and increase in sulfide in the effluent, it appears that sulfate reduction via SRB was occurring throughout the test in both barrels. Sulfide results for BCR 5 and 6 were up to 10 times higher than those observed in a similar study performed by EPA (CDM Smith, 2013a) where similar media were evaluated without pretreatment. With the exception of BCR 4 in round 5, BCRs 5 and 6 had higher sulfide in their effluent than all other tested reactors in this study.
Alkalinity in the ChitoRem® pretreatment stabilized at 1,500 mg/L as CaCO3 from rounds 3 to 5 (Figure 3‐17). BCR 5 followed a similar trend with alkalinity elevated to 2,000 mg/L in the last three rounds. BCR 6 added approximately an order of magnitude of alkalinity to its pretreated influent with a final alkalinity of 7,000 mg/L in round 5. BCR 5 had the highest increase of alkalinity of all woody substrate barrels and was clearly aided by the increase in alkalinity it received from the ChitoRem® pretreatment. BCR 6 was very similar to BCRs 2 and 4 in the first two rounds but was consistently higher in the last three rounds, indicating that the ChitoRem® pretreatment gave this BCR 6 system an advantage in alkalinity generation. Alkalinity generation in the ChitoRem® reactors was at least an order of magnitude greater than alkalinity generated in woody substrate barrels.
The ChitoRem® pretreatment reactor was not evaluated for VFA production (Figure 3‐20). Acetic acid was elevated in BCR 5 at 1,000 mg/L through rounds 2 to 4 then dropped to 30 mg/L in round 5. BCR 6 maintained acetic acid concentrations from 17,000 mg/L initially in round 1, dropping steadily to
3‐19 Section 3 Evaluation Criteria, Results, and Discussion
4,000 mg/L in round 5. Acetic acid in BCR 5 was clearly increased by the ChitoRem® pretreatment. The large drop at the end, although not seen with the other BCRs, could be influenced by the increased residence time and usage by SRB as electron donors. VFA generation in BCR 6 appears to be similar to the other ChitoRem® barrels discussed above.
Summary Overall, the woody substrate BCR 5 and ChitoRem® BCR 6 performed similarly and had some of the best MRE results in the test, with target removals met with Al, Cd, Cr, Cu, Fe, and Zn. As and Pb were too low in the MIW for an effective analysis to be performed using ORD MRLs. Both had poor performance with removal of Mn and Ni; however, BCR 5 was more successful in removing Ni while BCR 6 was more successful in removing Mn. Both reactors removed a sufficient fraction of Al and Fe; however, BCR 5 was more efficient in the removal of these two metals.
BCR 5 was the only woody substrate reactor that was able to effectively remove both Fe and Cr. BCR 5 had consistently lower ORP values, and higher sulfide production was observed throughout the test. It was clear that the ChitoRem® pretreatment enhanced the MRE of the system. BCR 6 had better Al removal than BCR 2; however, besides Al removal, BCR 2 and 6 were similar. All three ChitoRem® BCRs did not meet their removal benchmark for Mn or Ni, with BCR 4 performing the poorest with Mn and BCR 6 performing the poorest with Ni.
BCR 5 was the only woody substrate barrel that had an observed increase in THg. This increase is potentially a result of elevated THg in the BCR influent sourced from the ChitoRem® pretreatment barrel feeding BCR 5 and 6. The MeHg in effluent for BCR 5 is at the same magnitude as the effluent of BCR 2. BCR 2 and the ChitoRem® pretreatment barrel are of identical construction and both receive untreated MIW, so there is a potential that they would have similar Hg releases. The pretreatment barrels were not sampled for trace Hg, however, and further investigation is needed to make any concrete conclusions on the effects pretreatment has on the final effluent Hg concentrations. If Hg is indeed elevated in effluent from the ChitoRem®, it is unclear why it did not lead to higher effluent THg concentrations in BCR 6 relative to either BCR 2 or BCR 4; yet, BCR 6 had the highest MeHg effluent concentrations out of any BCR barrel in round 4. The flow rate in BCR 6 was at 0.2 L/hr when measured in round 5, 15 percent of the original design flow. It is unclear how the processes influencing the reduction in flow are affecting the increase and/or decrease in ChitoRem® matrix effluent. It is clear that Hg speciation dynamics is complicated in these biogeochemical reactors, and further investigation is required to help illuminate the fate and transport of Hg through these treatment scenarios. 3.2.5 ChitoRem® Permeability Each of the ChitoRem® reactors; the ChitoRem® pretreatment barrel; and BCRs 2, 4, and 6 had undisturbed sediment cores removed on two separate occasions and submitted for grain size and hydraulic conductivity testing, the results of which are reported in Appendix A. The first evaluation was conducted after round 5 immediately preceding a rebuild of the ChitoRem® reactors. The second evaluation was collected following the system rebuild and a 2‐ month period of no flow. Although the MIW stopped flowing after the rebuild, and the test was prematurely stopped, these sediment core analyses were used to evaluate the problems associated with reduced flow in these reactors and to assess the success of the system rebuild.
The grain size analysis for the four reactors pre‐rebuild showed that BCRs 2, 4, and 6 were within the size range for a classification of poorly graded sand with gravel (SP) and that the ChitoRem® pretreatment barrel was within the range of poorly graded sand with silt and gravel (SP‐SM). The
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increase in fines observed in the ChitoRem® pretreatment follows the observations when removing the media that the black reacted ChitoRem® extended throughout the media, whereas the black reacted media were isolated to the top 4 inches in the BCRs. In areas where the black media were observed, the media appeared to have a slimy quality, which most likely was due to the formation of a biofilm from microbial activity and an accumulation of precipitated fines from metal precipitation and protein degradation. These results most likely showed that the MIW did not have an opportunity to react with the entire barrel in the ChitoRem® BCRs.
The grain size analysis for the four reactors post‐rebuild and a 2‐ month period of stagnation showed that the ChitoRem® pretreatment barrel and BCRs 4 and 6 were all within the size range for a classification of poorly graded gravel with sand (GP), with BCR 2 remaining within the range of poorly graded sand with gravel (SP). Although there was a decrease in fines in all barrels post‐rebuild, there was still a black saturated gelatinous layer in the top several inches of the media overlaying a dark gray unsaturated media. The addition of gravel and homogenization decreased the sand by 20 to 30 percent, which also most likely explains the decrease in fines.
The permeability measured in the ChitoRem® pretreatment and BCRs 2, 4, and 6 pre‐rebuild were 1.1X10‐4, 1.8X10‐3, 9.7X10‐4, and 9.6X10‐5 centimeters per second (cm/sec), respectively. These measurements match observations that BCR 6 had the most problems maintaining design flow and continued to decrease in flow over the course of the test. The ChitoRem® pretreatment was similar to BCR 4, and both had issues with flow through the test. Increasing the head in the ChitoRem® pretreatment improved the flow for round 3, but then the system slowed to less than half the design flow in rounds 4 and 5. BCR 2 had the highest permeability after the test and was able to maintain design flow for most of the test, with performance deteriorating in round 5. The grain size analysis for the BCRs suggests that permeability should be within a range of well‐sorted sand and glacial outwash, 10‐3 to 10‐1 (Fetter 2001). The measured permeability was instead within a range consistent with silty and fine sands 10‐5 to 10‐3. Although BCR 2 fell between the two size classifications, it was apparent that the permeability in the reactor was steadily decreasing over time. It seemed that given the size of the initial substrate, the growth of biofilm, and the accumulation of fine precipitates, the current ChitoRem® substrate composition was not appropriate for this MIW at the prescribed flow rate to substrate volume. More experimentation is needed to determine a more appropriate starting ChitoRem® particle size, gravel and sand percentages, and reactor volume to flow ratios before a full scale system can be designed.
The permeability measured in the ChitoRem® pretreatment and BCRs 2, 4, and 6 were 1.9X10‐3, 2.3X10‐4, 6.9X10‐4, and 8.8X10‐4, respectively. Although the flow stopped days after the rebuild, the column tests show that permeability was improved in the ChitoRem® pretreatment barrel and BCR 6, which had the lowest permeability in the pre‐rebuild evaluation. However, BCRs 4 and 6 both had lower permeability after the rebuild. Considering that all barrels were homogenized and had equal quantities of pea gravel added to them during the rebuild, the differences in permeability may be more related to difference in growth of biofilm in the barrels during the stagnant period rather than grain size and composition. 3.3 Data Validation and Usability In accordance with the Formosa Treatability Study QAPP, a Level 2A data verification was performed. Laboratory results were reviewed for usability and limitations of the data and compliance with project objectives. Data were qualified in accordance with EPA CLP National Functional Guidelines for
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Inorganic Superfund Data Review, Final (EPA 2010) (NFGs), with method‐specific and treatability study requirements superseding the National Functional Guidelines.
A data evaluation memo is included in Appendix B to this report, summarizing the quality control data in terms of precision, accuracy, representativeness, comparability, completeness, and sensitivity, commonly referred to as the PARCCS parameters. Data were qualified as estimated (J) when accuracy or precision measurements were outside criteria established in the ORD laboratory QAPP. Sensitivity was impacted when target analytes were reported in the method blank and/or the field blank at concentrations above the MRLs. In these cases, when the sample result was less than or equal to the concentration reported in the blank, sample data were qualified as undetected. This was most prominent in sampling events round 4 and round 5 where sample data for both barium and zinc were qualified as undetected because blank concentrations were greater than the sample concentrations. This resulted in elevated MRLs in these instances. The NFGs indicate that data within 10 times the blank concentration are qualified as undetected; however, for the objectives of the treatability study, it was decided this would result in the loss of relevant data. Instead, results greater than the blank concentration but within 10 times the concentration reported in the blank were qualified as estimated with a possible high bias (J+).
No data were rejected in the course of the data evaluation and all data, as qualified, were considered usable.
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Section 4 Conclusions and Recommendations
This section summarizes the conclusions of the pilot‐scale treatability study and presents recommendations for modifications for a future designs. 4.1 Pilot‐Scale Treatability Study Conclusions Key observations:
. Target metals
o Cadmium target 90 percent MREs and potential water quality benchmark of 0.0035 mg/L were met with all treatment systems with the exception of BCR 1.
o Chromium target 90 percent MREs were met with all but BCRs 1 and 3 treatment systems through round 4. It is inconclusive if MREs were met with round 5 considering that the influent MIW dropped to within an 80 percent difference with the MRLs. BCR 1 was the only treatment system that had effluent above the potential water quality benchmark of 0.111 mg/L through most of the test; however, it was in compliance by round 5.
o Copper target 90 percent MREs were met with all barrels throughout the test. BCRs 1 and 3 were above the potential water quality benchmark of 0.012 mg/L for a majority of the test. BCR 3 dropped below the potential water quality benchmark in round 5.
o Lead was removed below MRLs over the entire course of the test. MRLs were too high to make a comparison with potential water quality benchmark of 0.0043 mg/L or to determine MREs.
o Nickel target 90 percent MREs were not met in any of the treatment systems by the end of this test. The woody substrate BCRs 1, 3, and 5 performed the best with MREs ranging from 50 to 91 percent, and BCR 6 performed the worst with MREs ranging from 44 to 60 percent. Nickel met the potential water quality benchmark in all systems; however, Ni in MIW was also below benchmark.
o Zinc target 90 percent MREs were met with all treatment systems with the exception of BCR 1. Potential water quality benchmark of 0.179 mg/L was not met in any system by round 5.
. Other metals:
o Aluminum target 90 percent MREs were met with all treatment systems in round 5. BCRs 2, 4, and 6 had several occurrences where their MREs dropped below 90 percent over the course of the test.
o Arsenic was dropped to below MRLs after an initial flush off of the ChitoRem® systems.
o Calcium was contributed to the MIW in all systems, with order of magnitude increases observed in ChitoRem® systems.
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o Cobalt was removed from MIW in all barrels to below MRLs with the exception of BCR 1.
o Iron target 90 percent MREs were met with all treatment systems with the exception of BCRs 1 and 3. BCR 1 removal of Fe was below 50 percent for a majority of the test.
o Manganese target 90 percent removal was not achieved with any treatment system in this study. The best removal was achieved with BCRs 2 and 6 with removals of 60 to 80 percent and worst with BCRs 1 and 3 with Mn addition observed up to 50 percent.
. Mercury:
o Total Mercury was elevated in all reactor effluents associated with the ChitoRem® media. Elevated mercury in these effluent streams were all elevated above concentrations typical for unmined basins around the United States and above established wastewater treatment total maximum daily loads of 1.3 ng/L (EPA 1995). The magnitude of release from the ChitoRem® substrate appears to be influenced by both MIW conditioning and flow.
o Methylmercury was elevated in all reactors associated with the ChitoRem® media. Influent concentrations were below MRL; therefore, MeHg was either generated in the reactor from the activity of sulfate‐reducing bacteria, or pre‐methylated MeHg was being released from the media. The concentration of MeHg in BCR 6 effluent, at 2.7 ng/L, is at the high end of the range found in mined basins around the United States (Scudder et al. 2009).
. ChitoRem® released higher concentrations of readily usable organics (such as acetic acid) compared to the woody mixture, and this was expected since the product comes from a living animal with protein Therefore, ChitoRem® BCRs produced lower ORPs and better sulfate reduction and metal removal. SAPS pre‐treatment appeared to facilitate the establishment of SRB in BCR 3 with the lower ORPs in BCR 3; thus, BCR 3 achieved better metal removal compared to BCR 1.
Precipitation and biofilm at the shallow depth of the ChitoRem® and sand mixture system appeared to minimize the achievable flow through this type of system and prevented an evaluation of a full ChitoRem® system.
General Conclusions . Overall, BCRs 4, 5, and 6 had the most consistent and elevated MRE for Cd, Cr, Cu, Ni, and Zn. All three were able to maintain an MRE of well over 90 percent consistently after system stabilization. Out of these three treatment systems, BCR 5 had more effective removal of target metals Cd and Cu, and although none of the three met target removal with Ni, BCR 5 came the closest with MREs greater than 85 percent for a majority of the test. BCR 5 was also able to more effectively remove other major metals present in significant concentrations such as Al and Fe. BCR 5 had the highest sulfide concentration in its effluent and had as equal to or lower ORP than the ChitoRem® BCRs 4 and 6 over the course of the test. With the high amount of limestone and CaCO3 materials corresponding to increases in alkalinity and increased sulfate reduction metrics, the mechanism of metals removal that is most likely dominant in these systems was CaCO3 dissolution with subsequent metal oxy‐hydroxide and/or carbonate precipitation. These reactions are followed later by sulfate reduction and sulfide generation, with subsequent metal sulfide complexation/precipitation.
4‐2 Section 4 Conclusions and Recommendations
. The superior performance observed in the BCR 5 system appears to be a result of the combined treatment effect of a ChitoRem® reactor followed by a woody substrate barrel. Of the three woody substrate barrels, BCR 5 was the only reactor that had influent with consistently reduced ORP values, <‐200 mV. VFA production was low in both BCR 1 and BCR 3. VFAs were elevated in barrels with ChitoRem® in the system, either as a BCR barrel or a pretreatment. The fermentation of crab shell chitin is a well‐known source of VFAs. The short chain organic compounds of VFAs can be readily used as an electron donor for SRBs, and in the case with BCR 5, helped induce SRB activity. Manure, which compromises 20 percent of the woody substrate mixture, typically is a good source for SRB; however, it was important to provide optimum conditions for the organisms to prosper. Although BCR 2 was almost as effective as BCR 4 and BCR 6 with MRE, it struggled with Al removal and had the lowest sulfide production out of the ChitoRem® reactors. It follows that a way to ensure optimal performance in a ChitoRem® reactor would be to incorporate a pre‐treatment step that increases the pH and lowers the reduction potential.
. Considering that flow was an issue with the ChitoRem® media in this test, it follows that the observed decrease in performance in the ChitoRem® pretreatment was related to the pretreatment barrels receiving 2 times the flow as the BCRs. In future tests, matching flow in pretreatment and subsequent BCRs should be included in the design along with other flow improvement measures.
. BCR 2, although it had difficulty meeting the 90 percent target for Ni and Al, performed nearly as well as the top three treatment barrels discussed above. Although all ChitoRem® BCR systems were not able to meet the removal goals with Ni, BCR 2 had higher removal than BCR 6. One concern with a ChitoRem® reactor with no pretreatment moving forward was the issue concerning flow. The resolution to this issue could be to incorporate higher percentages of large inert media, such as gravel, which will lower the overall percent of reactive ChitoRem® material. This will most likely not be a problem considering observation when the system was dissected showed that much, if not most, of the ChitoRem® media were unreacted, and strategies that increase the permeability of the media will most likely improve the system’s performance. Another potential strategy to increase media permeability is to acquire ChitoRem® at a larger mesh size.
. The ChitoRem® substrate size fraction, composition, and reactor size had persistent issues maintaining design flow over the course of the test. Permeability testing of sediment cores from the reactors show hydraulic conductivity of a silty sand, and observation in the field and observed formation of biofilm suggest that the flow may not have recovered. The reduced flow and subsequent increased residence time within each reactor complicate the evaluation of the reactors. Further testing is needed to develop an ideal ChitoRem® mix, perhaps with a larger‐ sized crab shell grind and a higher percentage of inert material such as sand and gravel would add sufficient porosity. This will need to be experimentally determined either in the field prior to construction, or in the laboratory.
. The ChitoRem® and sand matrix was a source of THg to the effluent of this treatability test and either was a source of MeHg or provided conditions conducive to the conversion of resident Hg(II) to MeHg. The results reported in this study suggest that water chemistry and flow rate may play a significant role in the magnitude of THg release from the ChitoRem® and sand
4‐3 Section 4 Conclusions and Recommendations
matrix. Concentrations of THg, and in particular MeHg, observed in this treatability study are elevated and could potentially pose a risk to biological receptors in receiving surface waters.
. An unanticipated pump test prematurely ended the treatability test approximately half way through the experiment. Measures to improve that permeability of the ChitoRem® material had been completed after round 5 where the ChitoRem® material was removed from the reactor vessel and mixed with gravel. The test would have run 2 more months following the rebuild where potentially the ChitoRem® BCRs, if but it is impossible say whether or not the system would have rehabilitated if the flow had continued.
. There was strong evidence both in this treatability test and in others cited previously that ChitoRem® had the ability to increase pH and enhance metals removal from MIW. There was further evidence presented that using a ChitoRem® pretreatment reactor for a woody substrate BCR was the most optimal combination. However, there is still a persistent data gap in the ideal design of a ChitoRem® reactor to be able to achieve an optimal flow over a long period of time. The configurations evaluated in this test were not adequate for maintaining flow with this MIW. Therefore, further testing is needed prior to a full scale design.
. More experimentation is needed to determine a more appropriate starting ChitoRem® particle size, gravel and sand percentages, and reactor volume to flow ratios before a full scale system can be designed.
. The sulfate loading to BCR 1 and BCR 3 appeared to be at the high end since the organics released from the woody mixture were not able to fully reduce sulfate concentrations. A lower sulfate loading might improve the performance of the woody mixture. 4.2 Considerations for Future Design ChitoRem® Substrate Adjustment The ChitoRem® mixture will need adjusting if future studies performed with Formosa Mine MIW are considered. The current configuration had persistent issues maintaining sufficient porosity for effective flow through. Some potential solutions include increasing the grain size of the ChitoRem® material and increasing the percent by volume of the inert pea gravel. Considering that this will most optimally be done experimentally, a field or laboratory porosity test should be conducted prior to a future installation. The ChitoRem® material swells when hydrated, and therefore any porosity test should be conducted after hydration and the 2 week incubation period. After which, the hydrated media should be mixed at different ratios of pea gravel and placed in a column and tested for flow of MIW. Other measures to avoid preferential flow paths should also be considered. Layering zones of high permeability, such as coarse gravel, through the column in between layers of media should be considered.
The MIW entered the system at concentrations between 60 and 70 mg/L, and toxic effects on SRBs have been observed with zinc concentrations of 20 to 25 mg/L and greater (EPA 2006). This factor may have had the greatest impact on BCR 1, the untreated woody substrate, with already less than ideal conditions for SRB growth as demonstrated by low VFA and sulfide output. The performance of either system could be potentially enhanced by having a pre‐treatment step that reduces the elevated zinc load to the sulfate‐reducing population.
Results from the ORD bench scale ChitoRem® study evaluating Formosa MIW should be incorporated with the results of this treatability study. The integration and analysis of these two data sets is
4‐4 Section 4 Conclusions and Recommendations
essential prior to any future design work considering the current uncertainty of an optimal ChitoRem® mix that would be compatible with this MIW.
Modification to Analytical Testing of Effluent and Substrate Future testing of systems involving pretreatment should include analysis of VFAs and sulfide of the pretreatment reactors. This will aid in determining the functioning of the pretreatment unit and define the water quality of the BCR influent.
Substrate of reactors should be tested for metals content and microbial speciation to better understand spatially where redox transition zones are located in the different configurations. By determining where vertically the transition zones for redox process are in the barrels, the size and shape of the reactor vessels can be more optimally designed to enhance sulfate reduction and induce greater metals precipitation, which is particularly important in BCRs without pretreatment.
The ChitoRem® substrate and sand should be further evaluated to determine the implications of its observed contribution of Hg to treated MIW effluent. Although mercury was only evaluated at one point in time by one laboratory two months into the test, the observed THg and MeHg in ChitoRem® BCR effluent was elevated enough to potentially pose a risk to biological receptors in receiving surface waters. A Hg evaluation should include an analysis of both the ChitoRem® media and sand for both THg and MeHg and a study to determine what factors impact the magnitude of the size and longevity of the release of THg and MeHg to treated MIW effluent.
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Section 5 References
Al‐Abed, S. 2013. Personal Communication.
Benner, S.G., D.W., Blowes, W.D., Gould, R.B., Berbert Jr., C.J., Ptacek. Geochemistry of a permeable reactive barrier for metals and acid mine drainage. Environmental Science and Technology. 33, 2793‐ 2799.
Bohm, H.L., B.L., McNeal, G.A., O’Connor. 2001. Soil Chemistry: 3rd Ed. Wiley, New York.
CDM Smith 2013a. Draft Treatability Study Technical Memorandum for Remedial Investigation/Feasibility Study, Blue Ledge Mine Superfund Site, Siskiyou County, California, May.
______2013b. Draft Treatability Study Work Plan for Operable Unit 2 Remedial Investigation/Feasibility Study, Formosa Mine Superfund Site, Douglas County, Oregon, June.
CDM Smith 2012. Final OU1 Remedial Investigation Report, Formosa Mine Superfund Site, Douglas County, Oregon. January.
Davison, W. 1993. Iron and manganese in lakes. Earth‐Science Reviews. 34, 119‐163.
EPA 2010. National Functional Guidelines for Inorganic Superfund Data Review. USEPA‐540‐R‐10‐ 011. January
EPA 2006. Bioremediation of Acid Mine Drainage Using Sulfate‐Reducing Bacteria. NNEMS report for EPA. Washington DC. August.
EPA 1992. Guidance for Conducting Treatability Studies under CERCLA. Final. EPA/540/R‐92/071a. October.
Fetter, C.W. 2001. Applied Hydrogeology: 4th Ed. Prentice‐Hall, Inc. New Jersey.
Hart Crowser. 2000. Removal Assessment: Focused Engineering Evaluation and Cost Analysis, Formosa Abandoned Mine Land Site, Douglas County, Oregon. September.
Neculita, C.M., Zagury, G.J. 2008. Biological treatment of highly contaminated acid mine drainage in batch reactors: Long‐term treatment and reactive mixture characterization. Journal of Hazardous Materials. 157, 358‐366.
Robinson‐Lora, M.A., R.A. Brennan. 2010. Biosorption of manganese onto chitin and associated proteins during the treatment of mine impacted water. Chemical Engineering Journal. 162, 565‐572.
Robinson‐Lora, M.A., R.A. Brennan. 2009. Efficient metal removal and neutralization of acid mine drainage by crab‐shell chitin under batch and continuous‐flow conditions. Bioresource Technology, 100, 5063‐5071.
Scudder, B.C., L. C. Chasar, D.A. Wentz, N.J. Bauch, M.E. Brigham, P.W. Moran, D.P. Krabbenhoft. 2009. Mercury in Fish, Bed Sediment, and Water from Streams Across the United States, 1998–2005; U.S.
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Geological Survey Scientific Investigation Report 2009‐5109; U.S. Geological Survey: Middleton, WI, USA.
Sun, Q., L.M., McDonald, J.G., Skousen. 2000. Effects of armoring on limestone neutralization of AMD. In: Proceedings, West Virginia Surface Mine Drainage Task Force Symposium, April, West Virginia University, Morgantown, WV. 93‐102.
United States Environmental Protection Agency (USEPA). 1995. 60 FR 15366. Final Water Quality Guidance for the Great Lakes Systems.
Venot, C., L., Figueroa, R.A., Brennan, T.R., Wildeman, D.J. Reisman, and M. Sieczkowski. 2008. Bench‐ scale removal comparing chitin and organic substrate on the national tunnel waters in Blackhawk, Colorado: Unusual manganese removal. In Proceedings: National Meeting of the American Society of Mining and Reclamation. Richmond VA, New Opportunities to Apply Our Science. June.
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Tables
Table 1‐1 Formosa 1 Adit Water Quality Data Location FORMOSA ADIT Sample Date 10/19/2009 1/26/2010 10/25/2010 1/26/2011 9/26/2011 2/13/2012 9/13/2012 Seep/Stream ADIT ADIT ADIT ADIT ADIT ADIT ADIT Total/Dissolved TDTDTDT D TDTDTD Chemical UnitsResult Q Result Q Result Q Result Q Result Q Result Q Result Q Result Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum µg/L8,980 9,240 25,200 27,700 9,550 9,340 21,200 21,700 13000 13000 29300 29000 11600 J 11800 Antimony µg/L0.35 U 2.0 U 10.1 10.0 2.0 U 2.0 U 5.7 5.4 7.3 J 6.7 J 60 U 60 U 60 U 60 U Arsenic µg/L5.4 2.8 167 167 6.1 3.8 124 118 56.8 J 32.6 J 121 95.5 50.3 29.4 Barium µg/L10.2 10.4 13.5 11.9 9.4 J 9.2 J 13.2 10.7 200 R 200 R 200 UJ 200 U 200 U 200 U Beryllium µg/L0.25 J 0.23 J 0.48 J 0.49 J 0.2 J 0.23 J 1.0 U 1.0 U 0.35 J 0.32 J 0.49 J 0.48 J 5 U 5 U Boron µg/L100 U 100 U 12.0 U 14.3 U 11.7 J 12.6 J 100 U 100 U 100 U 100 U Cadmium µg/L132 130 651 666 133 131 367 366 219 J 213 J 360 J 353 J 139 185 Calcium µg/L171,000 178,000 58,600 64,700 J 180,000 178,000 71,700 72,200 102000 104000 98600 99000 103000 103000 Chromium µg/L2.7 2.7 18.1 18.4 2.4 2.0 13.3 13.7 10 U 10 U 11.8 12.8 3.9 J 3.9 J Cobalt µg/L15.5 15.4 19.8 20.5 14.6 14.6 13.6 13.7 15.5 J 14.8 J 19.8 J 50 U 50 U 50 U Copper µg/L3,170 3,150 44,000 42,800 2,710 2,700 31,500 32,200 5520 5400 31800 29900 3350 4360 Iron µg/L87,000 74,700 239,000 264,000 104,000 88,600 186,000 187,000 163000 164000 244000 J 247000 148000 142000 Lead µg/L16.3 15.3 74.0 78.2 16.2 14.6 73.6 73.6 35.2 J 32.9 J 94.9 83.5 34.2 32.6 Lithium µg/L100 U 100 U 16.6 U 18.1 U 13.9 J 15.8 J 100 U 100 U 14.9 J 14.5 J Magnesium µg/L24,300 25,000 21,100 23,200 J 25,400 25,300 20,100 20,000 23900 23800 27900 28600 21300 20800 Manganese µg/L2,340 2,280 2,090 J 2,150 2,280 2,310 1,750 1,770 2280 2230 2290 2290 1710 2100 Mercury µg/L0.2 U 0.2 U 0.2 U 0.2 U 0.2 U 0.2 U 0.2 U 0.2 U 0.056 J 0.2 U 0.2 U 0.2 U 0.2 U 0.2 U Molybdenum µg/L1.0 U 1.0 U 1.0 1.1 1.0 U 0.26 U 1.0 U 1.0 U NM NM Nickel µg/L70.7 71.0 76.4 80.2 63.3 63.6 58.4 58.9 76 74.1 68.1 J 59.5 J 48.4 56.6 Potassium µg/L1,960 J 2,040 J 625 J 714 J 1,980 J 1,960 J 801 J 816 1880 J 1870 J 5000 5000 U 2610 J 2460 J Selenium µg/L1.7 J 1.2 J 2.4 J 3.3 J 0.47 U 0.59 U 1.3 J 1.2 J 6.8 J 2.1 J 2 J 1.9 J 1 J 1.2 J Silver µg/L0.05 J 0.1 U 0.61 0.38 0.078 J 0.067 J 0.22 J 0.12 J 7.7 J 7 J 0.17 J 0.13 J 0.1 U 0.1 U Sodium µg/L11,000 11,500 5,890 6,240 9,670 9,570 5,560 5,990 9160 9130 7720 7660 11100 10900 Thallium µg/L0.51 J 0.48 J 0.63 J 0.66 J 0.71 J 1.3 1.0 U 1.0 U 4.3 J 4 J 25 U 25 U 25 U 25 U Thorium µg/L1.0 U 0.27 U 0.54 J 0.51 U 1.0 U 0.37 U 1.0 U 1.0 U NM NM Uranium µg/L0.63 J 0.59 J 3.6 3.7 0.71 J 0.69 J 2.2 2.2 NM NM Vanadium µg/L5.0 U 5.0 U 13.2 14.8 1.4 U 0.89 U 5.0 U 5.0 U 5.8 J 5.3 J 11.6 J 11.3 J 50 U 50 U Zinc µg/L61,900 61,200 140,000 146,000 60,800 61,500 85,600 88,100 70300 72200 100000 104000 60300 68600 General Chemistry Acidity by titration mg/L340 1,200 400 J 490 J840 440 Alkalinity, Total1 mg/L5.0 U 5.0 U 5.0 5.0 U 5 U 5 U 5 U Ammonia as N (distilled) mg/L0.5 U 0.44 J 1.01 J 0.41 J 1.06 Chloride mg/L 1.97 1.69 3.572.6 J 3.52 1.79 3.07 Fluoride mg/L 0.585 1.52 1.441.32 1.73 1.75 1.55 547 257 549 263 Nitrogen, Nitrate‐Nitrite mg/L0.05 U 0.0605 0.05 0.0561 0.05 U Sulfate mg/L 947 1,560 9481,070 908 1240 807 Total Dissolved Solids mg/L1,450 2,340 1,390 1,510 1480 2020 1240 Total Suspended Solids mg/L99.5 2.1 98.5 3.74 2.116.4 10.1
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 2 Table 1‐1 Formosa 1 Adit Water Quality Data Location FORMOSA ADIT Sample Date 10/19/2009 1/26/2010 10/25/2010 1/26/2011 9/26/2011 2/13/2012 9/13/2012 Seep/Stream ADIT ADIT ADIT ADIT ADIT ADIT ADIT Total/Dissolved TDTDTDT D TDTDTD Chemical UnitsResult Q Result Q Result Q Result Q Result Q Result Q Result Q Result Q Results Q Results Q Results Q Results Q Results Q Results Q Field Parameters Alkalinity, Total1 mg/L5.0 < 5.0 < 5.0 < 5.0 < 5 U 5 5 U Conductivity µS/cm1,708 1,925 2,543 4,185 1483 2208 1092 Dissolved Oxygen mg/L9.85 1.03 11.91 1.07 0.091.62 0.73 Ferrous Iron mg/L3.3 > 19.23 5.13 7.53 22.48.12 12.9 Flow gpm2.0 42.91 0.8 29.94 313.4 2.5 ORP mV464 472 429 431 353.6400 359.3 pH su2.98 2.15 3.13 2.85 3.312.71 3.26 Temperature deg C9.66 9.56 7.17 9.58 9.469.55 9.5
Notes: deg C ‐ degrees Celsius gpm ‐ gallon per minute J ‐ Estimated value mg/L ‐ milligram per liter mV ‐ millivolt NM ‐ not measured ORP ‐ oxidization reduction potential Q ‐ Laboratory qualifier R ‐ Rejected value su ‐ standard unit U ‐ Below detection limit (reporting limit shown) µg/L ‐ microgram per liter µS/cm ‐ microSiemens per centimeter
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 2 of 2 Table 1‐2 Composition of Pre‐Treatment Materials Pre‐Treatment SAPS Pre‐Treatment ChitoRem® Composition Substrate Mix (v/v Volume Substrate Mix (v/v Percent) (gallon) Percent) Volume (gallon) Compost 12.50 4.38 ‐‐ ‐‐ Fresh dairy manure 12.50 4.38 ‐‐ ‐‐ Limestone chips 3/4‐inch to 1.5‐inch 75.00 26.25 ‐‐ ‐‐ 3/4‐inch inert gravel ‐‐ 7.50 ‐‐ 7.50 ChitoRem® ‐‐ ‐‐ 40 14.00 Construction sand ‐‐ ‐‐ 40 21.00 Inert pea gravel ‐‐ ‐‐ 20 7.00 Total 100.00% 42.51 100 49.50
Table 1‐3 BCR and Pre‐Treatment Substrate Percentages and Volumes Woody Material Mixture ChitoRem® and Sand Mixture Composition Substrate Mix (v/v Volume Substrate Mix (v/v Percent) (gallon) Percent) Volume (gallon) Sawdust 15.00 5.25 ‐‐ ‐‐ Wood chips 30.00 10.50 ‐‐ ‐‐ Compost 15.00 5.25 ‐‐ ‐‐ Fresh dairy manure 20.00 7.00 ‐‐ ‐‐ Limestone chips 3/4‐inch to 1.5‐inch 20.00 7.00 ‐‐ ‐‐ 3/4‐inch inert gravel ‐‐ 7.50 ‐‐ 7.50 ChitoRem® ‐‐ ‐‐ 40.00 14.00 Construction sand ‐‐ ‐‐ 40.00 21.00 Inert pea gravel ‐‐ ‐‐ 20.00 7.00 Total 100.00 42.50 100.00 49.50
Page 1 of 1 Formosa Mine Superfund Site OU2, Douglas County, Oregon
Table 2‐1 Headspace Concentrations after One Month Stagnation Period 3 3 Treatment Reactor H2S, mg/m *Methane, mg/m SAPS 0 18 ChitoRem® Pretreatment 5 >3611 BCR 1 0 >3611 BCR 2 30 >3611 BCR 3 0 435 BCR 4 0 >3611 BCR 5 0 >3611 BCR 6 0 >3611 *Upper Detection Limit = 3611 mg/m3
Page 1 of 1 Formosa Mine Superfund Site OU2, Douglas County, Oregon Table 2‐2 Formosa Treatability Study Sampling and Analysis Summary Prelim Round Round 1 Round 2 Round 3 Area Well ID 5/2/2013 7/10/2013 7/23/2013 8/6/2013 Formosa Sulfide, Ammonia, Dissolved Metals, TSS, THg and DHg (1631), TMeHg Treatability Adit Sulfates, Alkalinity, VFA and DMeHg (1630) Full analysis w/o Sulfide THg and DHg (7470) Full Analyses THg and DHg (7470) Full Analyses Study BCR1 Full analysis w/o Sulfide THg and DHg (7470) Full Analyses THg and DHg (7470) Full Analyses BCR2 Full analysis w/o Sulfide THg and DHg (7470) Full Analyses THg and DHg (7470) Full Analyses BCR3 Full analysis w/o Sulfide THg and DHg (7470) Full Analyses THg and DHg (7470) Full Analyses BCR4 Full analysis w/o Sulfide THg and DHg (7470) Full Analyses THg and DHg (7470) Full Analyses BCR5 Full analysis w/o Sulfide THg and DHg (7470) Full Analyses THg and DHg (7470) Full Analyses BCR6 Full analysis w/o Sulfide THg and DHg (7470) Full Analyses THg and DHg (7470) Full Analyses ChitPre Full oanalysis w/ Sulfide and VFA THg and DHg (7470) Full analysis w/o Sulfide and VFA THg and DHg (7470) Full analysis w/o Sulfide and VFA SAPS Full analysis w/o Sulfide and VFA THg and DHg (7470) Full analysis w/o Sulfide and VFA THg and DHg (7470) Full analysis w/o Sulfide and VFA
Round 4 Round 5 Area Well ID 8/20/2013 9/5/2013 Formosa THg and gDH (1631), TMeHg and Treatability Adit Full Analyses Full Analyses + Ammonia and TSS DMeHg (1630) Study BCR1 Full Analyses Full Analyses TMeHg (1630), THg (1631) BCR2 Full Analyses Full Analyses TMeHg (1630), THg (1631) BCR3 Full Analyses Full Analyses TMeHg (1630), THg (1631) BCR4 Full Analyses Full Analyses TMeHg (1630), THg (1631)
BCR5 Full Analyses Full Analyses TMeHg (1630), THg (1631) BCR6 Full Analyses Full Analyses TMeHg (1630), THg (1631) ChitPre Full analysis w/o Sulfide and VFA Full analysis w/o Sulfide and VFA SAPS Full oanalysis w/ Sulfide and VFA Full analysis w/o Sulfide and VFA
Notes: Full Analyses ‐ Total and Dissolved Metals, Anions, Sulfide, VFA THg (7470) ‐ Unfiltered Mercury Method 7470 DHg (7470) ‐ Filtered Mercury Method 7470 THg (1631) ‐ Unfiltered Trace Mercury Method 1631 TMeHg (1630) ‐ Unfiltered Trace Methylmercury Method 1630 DHg (1631) ‐ Filtered Trace Mercury Method 1631 DMeHg (1630) ‐ Filtered Trace Methylmercury Method 1630 TSS ‐ Total Suspended Solids Total and Dissolved Metals ‐ Aluminum, Antimony, Arsenic, Arsenic, Barium, Beryllium, Cadmium, Calcium, Chromium, Cobalt, Copper, Iron, Lead, Magnesium, Manganese, Nickel, Potassium, Selenium, Silver, Sodium, Thallium, Vanadium, Zinc Anions ‐ Chloride, Fluoride, Sulfate VFA Acetic, Propionic, iso‐Butyric, Butyric iso‐Valeric, Valeric, iso‐Caproic, Caproic, Heptanoic
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table 2‐3 Formosa Treatability Study Field Activity Timeline Activity Treatability Study Treatability study site construction June 16 ‐ 21, 2013 Media incubation period June 21 ‐ July 8, 2013 Flow through initiation July 8, 2013 Round 1 Maintenance and Influent/Effluent Sampling July 8 ‐ 10, 2013 Round 2 Maintenance and Influent/Effluent Sampling July 22 ‐ 23, 2013 Round 3 Maintenance and Influent/Effluent Sampling August 5 ‐ 6, 2013 Interim Surface water Round August 18, 2013 Round 4 Maintenance and Influent/Effluent Sampling August 19 ‐ 20, 2013 Round 5 Maintenance and Influent/Effluent Sampling September 3 ‐ 4, 2013 Round 6 Maintenance and Influent/Effluent Sampling NA Round 7 Maintenance and Influent/Effluent Sampling NA Round 8 Maintenance and Influent/Effluent Sampling NA Interim Surface Water Round October 23, 2013 Round 9 Maintenance and Influent/Effluent Sampling NA
Notes: NA ‐ not applicable
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table 3‐1 Surface Water Quality Comparison Values Dissolved Criteria (µg/L)* Metal In work plan Cadmium 0.355 Chromium III4 111 Copper 12.01 Lead 4.35 Nickel 79 Silver 0.102, 5 Zinc 1793 *Study results will be compared to surface water values for protection of freshwater aquatic life with chronic exposure. The criteria are hardness dependent and derived from updated Tables 20, 33A, and 33B, Jan. 31, 2013 per OAR 340‐041‐0033. A site‐specific hardness of 163 mg/L as calcium carbonate from Middle Creek analytical results was used to calculate the criteria for comparative use in this study. 1. Copper is reported with the Oregon default value based upon hardness of 100 milligrams per liter (mg/L). 2. Silver is not hardness dependent. 3. Value for zinc is National Recommended Water Quality Criteria (2009) adjusted for site‐specific hardness and is less than the Oregon chronic standard of 239 micrograms per liter (µg/L). 4. Total chromium will be measured. 5. Method reporting limits provided by ORD are greater than the dissolved criteria and may not allow direct comparison to the criteria.
Page 1 of 1 Formosa Mine Superfund Site OU2, Douglas County, Oregon Table 3‐2 Analytical Results Round 1 ‐ July 15, 2013
Base Reporting Location Limit Field Blank Method Blank Adit 01‐09 ChitRem Pre 01‐07 SAPS Pre 01‐08BCR1 01‐01 BCR2 01‐02 BCR3 01‐03 BCR4 01‐04 BCR5 01‐05 BCR6 01‐06 Total/Dissolved TDTDTDTDTD TD TD TDTDTDTD Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.105 0.105 U 0.095 U 0.105 U 14.1 14.2 1.02 0.755 0.954 0.095 1.05 0.095 4.49 4.2 1.61 0.34 3.52 3.06 2.11 1.23 4.8 4.8 Antimony mg/L 0.106 0.106 U 0.095 U 0.106 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.04 0.04 U 0.036 U 0.04 U 0.052 0.036 U 0.055 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 1.48 1.49 0.04 U 0.036 U 0.895 0.903 U 0.09 0.054 1.58 1.5 Barium mg/L 0.017 0.017 U 0.015 U 0.017 U 0.016 J+ 0.0172 0.202 J+ 0.148 0.149 J+ 0.075 0.213 J+ 0.056 0.672 J+ 0.532 0.486 J+ 0.283 0.495 J+ 0.407 0.697 J+ 0.423 0.679 J+ 0.588 Cadmium mg/L 0.003 0.003 U 0.002 U 0.003 U 0.192 0.194 0.003 U 0.002 U 0.014 0.003 0.011 0.002 U 0.021 0.016 0.019 0.002 U 0.02 0.005 0.013 0.002 U 0.03 0.025 Calcium mg/L 0.285 0.285 U 0.257 U 1.27 96.6 98 1,010 883 198 191 241 238 3,020 3,390 397 381 2,310 2,500 1,170 1,110 3,530 3,750 Chromium mg/L 0.024 0.024 U 0.022 U 0.024 U 0.233 0.236 0.024 U 0.022 U 0.113 0.0981 0.039 0.022 U 0.035 0.0325 0.033 0.022 U 0.028 0.0227 0.032 0.022 U 0.045 0.0398 Cobalt mg/L 0.011 0.011 U 0.01 U 0.011 U 0.015 0.014 0.019 0.013 0.011 U 0.011 0.011 U 0.01 U 0.164 0.148 0.017 0.011 0.103 0.091 0.025 0.015 0.193 0.185 Copper mg/L 0.008 0.008 U 0.007 U 0.008 U 5.47 7.5 0.026 0.007 U 0.298 1.103 0.421 0.019 0.228 0.163 1.01 0.025 0.4 0.07 0.686 0.027 0.279 0.23 Iron mg/L 0.117 0.117 U 0.105 U 0.117 U 150 148 4.7 0.873 72 64.9 22 9.6 21.8 13.8 12.7 3.4 17.7 9.34 12.9 3.58 28.2 19.8 Lead mg/L 0.019 0.019 U 0.017 U 0.019 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.011 0.011 U 0.01 U 0.33 21.9 21.8 155 127 52.4 49.7 114 118 917 849 251 241 745 690 490 462 1,100 1,040 Manganese mg/L 0.016 0.016 U 0.014 U 0.016 U 2.06 2.09 0.592 0.437 3.04 2.95 3.19 2.91 2.36 2.16 3.64 3.01 1.71 1.56 5.07 4.04 2.52 2.37 Mercury mg/L 0.139 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U Nickel mg/L 0.005 0.005 U 0.004 U 0.005 U 0.048 0.049 0.029 0.022 0.016 0.016 U 0.014 0.015 U 0.3223 0.313 0.044 0.035 0.21 0.202 0.061 0.052 0.402 0.398 Potassium mg/L 0.945 0.945 U 0.852 U 1.1 1.84 2.32 88.9 76 76.4 74 496 532 730 693 1,040 1,010 780 738 1,240 1,200 991 937 Silver mg/L 0.003 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U Sodium mg/L 1.52 1.52 U 1.371 U 1.52 U 8.03 7.98 106 69.1 18 16.8 96.1 100 1,780 2,290 207 205 1,480 1,560 361 368 2,100 2,700 Vanadium mg/L 0.029 0.029 U 0.026 U 0.029 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.038 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.043 0.039 Zinc mg/L 0.006 0.009 0.009 0.006 U 62.1 72.5 0.159 0.058 12.1 8.64 3.88 0.121 1.05 0.56 6.64 0.193 2.63 0.32 5.92 0.195 0.924 0.606 General Chemistry Alkalinity, Total1 mg/L 5 60 NR 5 U 5,000 400 2,000 30,000 5,000 20,000 13,000 32,000 pH SU NA 4.52 NR 3.18 7.25 6.09 6.36 6.51 6.67 6.82 6.71 6.87 Sulfide mg/L 0.01 NR NR NR NR NR NR NR NR NR NR Chloride mg/L 1.14 1.14 U 0.114 U 4.48 18.76 11.01 75.12 3,800 242 2,470 332 4,613 Fluoride mg/L 0.22 0.22 U 0.22 U 1.26 0.22 U 0.49 0.22 U 0.22 U 0.22 U 0.22 U 0.22 U 0.22 U Sulfate mg/L 3.31 3.31 U 0.331 U 1,765 679 801 719 1,367 421 948 344 1,284 Volatile Fatty Acids Acetic acid mg/L 3 3 U 0.98 U 781 13,400 1,572 7,760 5,280 16,680 Propionic acid mg/L 3.9 3.9 U 0.28 U 233 1,778 J 512 2,140 J 1,069 J 2,663 J iso‐Butyric acid mg/L 4.4 4.4 U 0.17 U 44 U 1,054 J 62.7 549.5 343.3 1,222 J Butyric acid mg/L 4.4 4.4 U 0.23 U 136 2,946 J 182.7 1,464 J 850 3,547 J iso‐Valeric acid mg/L 5.3 5.3 U 0.19 U 53 U 1,611 J 105 786 564 1,834 J Valeric acid mg/L 5.3 5.3 U 0.19 U 53 U 161 41.4 130 147 315 iso‐Caproic acid mg/L 5.8 5.8 U 0.2 U 58 U 473 9.36 251 66.5 500 Caproic acid mg/L 5.8 5.8 U 0.19 U 58 U 58 U 58 U 58 U 58 U 58 U Heptanoic acid mg/L 6.6 6.6 U 1.76 66 U 66 U 66 U 66 U 66 U 66 U
Notes: 1 ‐ units are mg/L as CaCO3 deg C ‐ degrees Celsius gal/min ‐ gallons per minute J ‐ Estimated value mg/L ‐ milligrams per liter mV ‐ millivolts ORP ‐ oxidation‐reduction potential Q ‐ Laboratory qualifier su ‐ standard units U ‐ Below detection limit (reporting limit shown) µg/L ‐ micrograms per liter µS/cm ‐ microSiemens per centimeter
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table 3‐2 Analytical Results Round 2 ‐ July 23, 2013
Base Reporting Location Limit Field Blank Method Blank Adit 02‐09 ChitRem Pre 02‐07 SAPS Pre 02‐08 BCR1 02‐01 BCR2 02‐02 BCR3 02‐03 BCR4 02‐04 BCR5 02‐05 BCR6 02‐06 Total/Dissolved TDTDTDT DT DTDTDTDT DTDTD Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.105 0.105 U 0.293 0.268 13.9 13.8 0.9 J+ 0.941 J+ 2.6 0.518 J+ 1.99 0.309 J+ 3.58 3.74 0.47 J+ 0.367 J+ 2.82 2.61 1.07 J+ 0.981 J+ 2.92 2.82 Antimony mg/L 0.106 0.106 U 0.095 U 0.106 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.04 0.04 U 0.036 U 0.04 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.264 0.29 0.04 U 0.036 U 0.098 0.052 U 0.04 U 0.036 U 0.053 0.036 U Barium mg/L 0.017 0.017 U 0.015 U 0.017 U 0.018 0.015 U 0.138 0.143 0.058 0.055 0.13 0.126 0.497 0.477 0.176 0.094 0.406 0.381 0.276 0.258 0.474 0.465 Cadmium mg/L 0.003 0.003 U 0.002 U 0.003 U 0.181 0.186 0.003 U 0.002 U 0.047 0.044 0.01 0.004 0.003 U 0.004 0.003 U 0.002 U 0.003 U 0.002 U 0.013 0.002 U 0.003 U 0.002 U Calcium mg/L 0.285 0.285 U 0.257 U 0.285 U 108 105 812 817 183 181 198 198 2,790 2,820 240 239 2,130 2,030 901 891 2,300 2,250 Chromium mg/L 0.024 0.024 U 0.022 U 0.024 U 0.264 0.261 0.024 U 0.022 U 0.228 0.215 0.212 0.21 0.024 U 0.014 0.072 0.069 0.024 U 0.022 U 0.024 U 0.022 U 0.024 U 0.022 U Cobalt mg/L 0.011 0.011 U 0.01 U 0.011 U 0.015 0.015 0.011 U 0.01 U 0.016 0.015 0.013 0.0125 0.04 0.043 0.011 U 0.01 U 0.018 0.012 0.011 U 0.01 U 0.011 U 0.01 U Copper mg/L 0.008 0.008 U 0.007 U 0.008 U 5.01 5.21 0.008 U 0.007 U 0.606 0.297 0.442 0.216 0.017 0.047 0.16 0.072 0.029 0.01 0.027 0.007 U 0.021 0.007 U Iron mg/L 0.117 0.117 U 0.105 U 0.117 U 158 152 2.89 0.143 140 133 127 126 6.34 6.27 45.2 43.6 4.99 2.68 0.658 0.105 U 2.87 0.622 Lead mg/L 0.019 0.019 U 0.017 U 0.019 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.011 0.011 U 0.01 U 0.011 U 23.1 22.5 39.4 38.7 25.4 25.5 26.2 26.3 371 352 33.8 32.9 216 191 65.5 57.4 149 146 Manganese mg/L 0.016 0.016 U 0.014 U 0.016 U 2.19 2.19 0.512 0.463 2.56 2.55 2.78 2.78 1.51 1.67 3.37 3.29 1.22 1.07 1.08 0.917 1.21 0.94 Mercury mg/L 0.139 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U Nickel mg/L 0.005 0.005 U 0.004 U 0.005 U 0.045 0.046 0.005 U 0.004 U 0.041 0.042 0.019 0.019 0.086 0.094 0.005 U 0.004 U 0.044 0.037 0.006 0.004 0.023 0.021 Potassium mg/L 0.945 0.945 U 0.852 U 0.945 U 1.89 1.81 4.33 5.01 5.82 6.28 9.31 8.72 218 232 25.3 19.9 179 169 51.9 42.3 37.4 36.1 Silver mg/L 0.003 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Sodium mg/L 1.52 1.52 U 1.371 U 1.52 U 8.2 8.21 11.6 13.4 8.4 8.74 9.24 9.2 342 407 11.3 10.3 134 105 30.3 27.1 81.1 83.3 Vanadium mg/L 0.029 0.029 U 0.026 U 0.029 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U Zinc mg/L 0.006 0.006 U 0.012 0.006 U 64.5 63.8 0.031 0.009 53.9 54 17.6 15.16 0.085 0.367 5.82 0.116 0.282 0.034 0.185 0.007 0.111 0.025 General Chemistry Alkalinity, Total1 mg/L 5 60 NR 5 U 2,800 125 200 17,800 375 14,000 3,900 11,700 pH SU NA 5.37 NR 3.3 6.85 5.33 5.96 6.74 6.23 6.82 6.79 6.58 Sulfide mg/L 0.01 0.01 U NR NR NR NR 0.33 3.7 2.9 3.1 39 10 Chloride mg/L 1.14 1.14 U 0.114 U 2.8 2.49 2.8 3.71 493 5.7 238 15.9 65.4 Fluoride mg/L 0.22 0.22 U 0.22 U 1.8 0.22 U 0.22 U 0.22 U 0.22 U 0.705 0.22 U 0.22 U 0.22 U Sulfate mg/L 3.31 3.31 U 0.331 U 1,893 541 821 987 180 547 97.4 288 67.2 Volatile Fatty Acids Acetic acid mg/L 3 3 U 3 U 29.6 9,967 85.7 6,378 1,150 8,162 Propionic acid mg/L 3.9 3.9 U 3.9 U 3.9 U 1,950 U 4.15 1,950 U 58.3 699 iso‐Butyric acid mg/L 4.4 4.4 U 4.4 U 4.4 U 2,200 U 4.4 U 2,200 U 44 U 176 Butyric acid mg/L 4.4 4.4 U 4.4 U 4.4 U 2,200 U 4.4 U 2,200 U 79.9 U 672 iso‐Valeric acid mg/L 5.3 5.3 U 5.3 U 5.3 U 2,650 U 5.3 U 2,650 U 66.5 282 Valeric acid mg/L 5.3 5.3 U 5.3 U 5.3 U 2,650 U 5.3 U 2,650 U 53 U 175 iso‐Caproic acid mg/L 5.8 5.8 U 5.8 U 5.8 U 2,900 U 5.8 U 2,900 U 58 U 145 U Caproic acid mg/L 5.8 5.8 U 5.8 U 5.8 U 2,900 U 5.8 U 2,900 U 58 U 145 U Heptanoic acid mg/L 6.6 6.6 U 6.6 U 6.6 U 3,300 U 6.6 U 3,300 U 66 U 165 U
Notes: 1 ‐ units are mg/L as CaCO3 deg C ‐ degrees Celsius gal/min ‐ gallons per minute J ‐ Estimated value mg/L ‐ milligrams per liter mV ‐ millivolts NR ‐ Not reported ORP ‐ oxidation‐reduction potential Q ‐ Laboratory qualifier su ‐ standard units U ‐ Below detection limit (reporting limit shown) µg/L ‐ micrograms per liter µS/cm ‐ microSiemens per centimeter
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table 3‐2 Analytical Results Round 3 ‐ August 6, 2013
Base Reporting Location Limit Field Blank Method Blank Adit 03‐09 ChitRem Pre 03‐07 SAPS Pre 03‐08 BCR1 03‐01 BCR2 03‐02 BCR3 03‐03 BCR4 03‐04 BCR5 03‐05 BCR6 03‐06 Total/Dissolved TDTDTDT D T DTDTDTDT DTDTD Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.105 0.135 0.161 0.105 U 13.6 13.4 0.449 J+ 0.511 J+ 3.91 0.5 J+ 3.19 0.988 J+ 2.03 1.9 0.242 J+ 0.245 J+ 1.48 1.54 0.473 J+ 0.46 J+ 2.71 2.48 Antimony mg/L 0.106 0.106 U 0.095 U 0.106 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.04 0.04 U 0.036 U 0.04 U 0.055 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.264 0.036 U 0.04 U 0.036 U 0.098 0.037 0.04 U 0.036 U 0.053 0.071 Barium mg/L 0.017 0.017 U 0.015 U 0.017 U 0.017 0.017 0.158 0.133 0.071 0.069 0.108 0.104 0.29 0.257 0.175 0.172 0.311 0.295 0.18 0.174 0.636 0.613 Cadmium mg/L 0.003 0.003 U 0.002 U 0.003 U 0.16 0.163 0.003 U 0.002 U 0.021 0.022 0.019 0.016 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U Calcium mg/L 0.285 0.322 0.257 U 0.285 U 111 110 496 489 183 190 198 188 2,790 1,490 240 228 2,130 1,270 901 506 2,300 1,970 Chromium mg/L 0.024 0.024 U 0.022 U 0.024 U 0.254 0.25 0.0766 0.069 0.217 0.213 0.206 0.202 0.024 U 0.022 U 0.116 0.107 0.024 U 0.022 U 0.024 U 0.022 U 0.024 U 0.022 U Cobalt mg/L 0.011 0.011 U 0.01 U 0.011 U 0.018 0.017 0.011 U 0.01 U 0.019 0.017 0.015 0.0141 0.011 U 0.01 U 0.011 U 0.107 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U Copper mg/L 0.008 0.008 U 0.007 U 0.008 U 4.39 4.43 0.08 0.0704 0.606 0.23 0.442 0.214 0.017 0.007 U 0.16 0.113 0.029 0.007 U 0.027 0.007 U 0.021 0.007 U Iron mg/L 0.117 0.117 U 0.105 U 0.117 U 153 159 49.2 45.4 134 138 131 125 2.18 0.21 76.9 69.6 2.67 1.96 1.56 0.12 1.49 0.622 Lead mg/L 0.019 0.019 U 0.017 U 0.019 U 0.04 0.041 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.011 0.044 0.01 U 0.011 U 22.8 23.4 38.6 38.3 23.7 24.2 24.7 24.2 73.8 70 26.8 26.2 76.5 75 40.3 40.1 104 132 Manganese mg/L 0.016 0.016 U 0.014 U 0.016 U 2.19 2.17 2.42 2.37 2.58 2.57 2.5 2.51 0.807 0.5 3.22 3.16 1.62 1.61 1.67 1.615 1.06 0.926 Mercury mg/L 0.139 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Nickel mg/L 0.005 0.005 U 0.004 U 0.005 U 0.041 0.042 0.005 U 0.004 U 0.036 0.038 0.021 0.021 0.011 0.01 0.005 U 0.004 U 0.013 0.013 0.005 U 0.004 U 0.019 0.024 Potassium mg/L 0.945 0.945 U 0.852 U 0.945 U 1.76 1.77 6.11 5.5 3.23 3.23 4.13 4.07 14 13 7.56 7.5 33 33 12.3 10.7 30.8 38 Silver mg/L 0.003 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U Sodium mg/L 1.52 1.52 U 1.371 U 1.52 U 8.94 9.1 19 16.9 9.17 9.25 9.26 9.24 26.6 26 9.29 9.5 40.3 41 19.3 18.9 62.6 103 Vanadium mg/L 0.029 0.029 U 0.026 U 0.029 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U Zinc mg/L 0.006 0.016 0.005 U 0.009 68.4 66.5 0.022 J+ 0.006 49.8 48.7 29.9 27 0.229 0.059 1.77 0.256 0.016 J+ 0.005 U 0.041 J+ 0.006 0.067 J+ 0.005 U General Chemistry Alkalinity, Total1 mg/L 5 60 NR 5 U 1,400 125 125 5,600 300 5,000 1,700 10,400 pH SU NA 5.26 NR 3.49 6.25 6.08 5.91 6.94 6.22 6.49 6.47 6.55 Sulfide mg/L 0.01 0.01 U NR NR NR NR 0.01 1.7 0.5 6.3 24 10 Chloride mg/L 1.14 1.14 U 0.114 U 3.53 6.72 2.86 3.25 6.53 2.88 21.2 10.5 69.3 Fluoride mg/L 0.22 0.22 U 0.22 U 2.1 0.22 U 1.66 1.76 0.22 U 1.06 0.22 U 0.22 U 0.22 U Sulfate mg/L 3.31 3.31 U 0.331 U 1,840 424 809 1,001 495 611 133 312 44.7 Volatile Fatty Acids Acetic acid mg/L 3 3 U 3 U 9.8 3,073 14.7 1,247 900 5,897 Propionic acid mg/L 3.9 3.9 U 3.9 U 3.9 U 780 U 3.9 U 390 U 97.5 U 724 iso‐Butyric acid mg/L 4.4 4.4 U 4.4 U 4.4 U 880 U 4.4 U 440 U 110 U 440 U Butyric acid mg/L 4.4 4.4 U 4.4 U 4.4 U 880 U 4.4 U 440 U 110 U 1,682 iso‐Valeric acid mg/L 5.3 5.3 U 5.3 U 5.3 U 1,060 U 5.3 U 530 U 132.5 U 530 U Valeric acid mg/L 5.3 5.3 U 5.3 U 5.3 U 1,060 U 5.3 U 530 U 132.5 U 530 U iso‐Caproic acid mg/L 5.8 5.8 U 5.8 U 5.8 U 1,160 U 5.8 U 580 U 145 U 580 U Caproic acid mg/L 5.8 5.8 U 5.8 U 5.8 U 1,160 U 5.8 U 580 U 145 U 580 U Heptanoic acid mg/L 6.6 6.6 U 6.6 U 6.6 U 1,320 U 6.6 U 660 U 165 U 660 U
Notes: 1 ‐ units are mg/L as CaCO3 deg C ‐ degrees Celsius gal/min ‐ gallons per minute J ‐ Estimated value mg/L ‐ milligrams per liter mV ‐ millivolts NR ‐ Not reported ORP ‐ oxidation‐reduction potential Q ‐ Laboratory qualifier su ‐ standard units U ‐ Below detection limit (reporting limit shown) µg/L ‐ micrograms per liter µS/cm ‐ microSiemens per centimeter
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table 3‐2 Analytical Results Round 4 ‐ August 20, 2013
Base Reporting Location Limit Field Blank Method Blank Adit 04‐09 ChitRem Pre 04‐07 SAPS Pre 04‐08 BCR1 04‐01 BCR2 04‐02 BCR3 04‐03 BCR4 04‐04 BCR5 04‐05 BCR6 04‐06 Total/Dissolved TDTD T DT D T DTDTDTDT DTDTD Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.105 0.105 U 0.218 0.105 U 13.6 J 13.6 0.42 J 0.285 3.78 J 0.695 1.51 J 0.486 1.79 J 1.52 0.105 UJ 0.183 1.11 J 0.81 0.483 J 0.219 1.34 J 1.07 Antimony mg/L 0.106 0.106 U 0.095 U 0.106 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.04 0.04 U 0.036 U 0.04 U 0.054 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 0.036 U Barium mg/L 0.017 0.017 U 0.495 0.017 U 0.017 U 0.174 U 0.128 0.536 J+ 0.063 0.203 U 0.072 0.184 U 0.376 0.714 J+ 0.132 0.267 U 0.255 0.595 J+ 0.143 0.6 J+ 0.366 0.706 J+ Cadmium mg/L 0.003 0.003 U 0.002 U 0.003 U 0.154 0.155 0.003 U 0.002 U 0.012 J+ 0.012 J+ 0.006 J+ 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U Calcium mg/L 0.285 0.285 U 0.257 U 1.71 117 112 411 393 203 191 194 188 1,654 1,530 244 235 1,122 913 467 445 1,310 1,220 Chromium mg/L 0.024 0.024 U 0.022 U 0.024 U 0.272 0.263 0.052 0.042 0.192 0.182 0.134 0.13 0.024 U 0.022 U 0.048 0.046 0.024 U 0.022 U 0.024 U 0.022 U 0.024 U 0.022 U Cobalt mg/L 0.011 0.011 U 0.01 U 0.011 U 0.012 J+ 0.012 J+ 0.011 U 0.01 U 0.014 J+ 0.011 J+ 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U Copper mg/L 0.008 0.008 U 0.007 U 0.008 U 4.24 4.14 0.051 0.041 0.287 0.185 0.249 0.134 0.01 0.007 U 0.046 0.043 0.011 0.007 U 0.013 0.007 U 0.008 U 0.007 U Iron mg/L 0.117 0.117 U 0.105 U 0.117 U 173 171 32.8 27.3 122 120 88.4 86.6 2.52 0.781 30 28.9 5.06 4.68 1.21 0.069 1.54 0.522 Lead mg/L 0.019 0.019 U 0.017 U 0.019 U 0.041 0.037 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.011 0.011 U 0.018 0.037 25.8 25.9 37 37.3 27.1 27.2 25.7 26 101 104 26.4 26.5 67.6 56.3 41.9 40.9 91.5 91.8 Manganese mg/L 0.016 0.016 U 0.014 U 0.016 U 2.24 2.15 2.29 2.14 2.57 2.45 2.21 2.12 0.851 0.713 2.52 2.43 2.04 2.02 1.5 1.39 0.776 0.669 Mercury mg/L 0.139 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Nickel mg/L 0.005 0.005 U 0.004 U 0.005 U 0.023 J+ 0.027 J+ 0.005 U 0.004 U 0.032 J+ 0.036 J+ 0.005 U 0.004 U 0.011 J+ 0.008 J+ 0.005 U 0.004 U 0.007 J+ 0.004 U 0.005 U 0.004 U 0.012 J+ 0.011 J+ Potassium mg/L 0.945 0.945 U 0.852 U 0.945 U 2.12 2.91 5.62 6.63 3.16 4.03 5.53 6.45 17.2 16.9 5.82 6.76 21 16.3 12.3 12.4 22.1 22.2 Silver mg/L 0.003 0.01 0.009 0.009 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.004 U 0.004 U 0.009 U 0.006 U 0.006 U 0.003 U Sodium mg/L 1.52 1.62 1.371 U 1.52 U 12.2 11.5 20.2 19.8 10.3 11.7 10.1 11.6 49.6 48.1 10.1 11.5 20.2 18.1 22.4 23.1 50.6 48.4 Vanadium mg/L 0.029 0.029 U 0.026 U 0.029 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U Zinc mg/L 0.006 0.006 0.284 0.006 U 66.5 66 0.024 J+ 0.286 U 55.2 52.8 13.2 13.9 0.055 J+ 0.19 U 1.95 0.458 J+ 0.331 0.209 U 0.083 J+ 0.261 U 0.026 J+ 0.186 U General Chemistry Alkalinity, Total1 mg/L 5 60 NR 5 U 1,430 60 250 6,300 300 5,900 1,750 7,300 pH SU NA 4.95 NR 3.51 6.38 6.08 6.07 6.7 6.29 6.42 6.6 6.54 Sulfide mg/L 0.01 0.01 U NR NR NR NR 0.01 U 1.5 0.08 1.9 20 4 Chloride mg/L 1.14 1.14 U 0.114 U 2.87 4.34 2.92 2.9 17.9 2.72 2.2 7.5 15.5 Fluoride mg/L 0.22 0.22 U 0.022 U 1.61 0.22 U 1.81 0.22 U 0.22 U 1.1 0.22 U 0.22 U 0.22 U Sulfate mg/L 3.31 3.31 U 0.331 U 2,180 114 916 670 118 440 120 32 3.31 U Volatile Fatty Acids Acetic acid mg/L 3 3 U 3 U 15.4 4,610 5.2 2,970 784 4,588 Propionic acid mg/L 3.9 3.9 U 3.9 U 3.9 U 780 U 3.9 U 390 U 97.5 U 780 U iso‐Butyric acid mg/L 4.4 4.4 U 4.4 U 4.4 U 880 U 4.4 U 440 U 110 U 880 U Butyric acid mg/L 4.4 4.4 U 4.4 U 4.4 U 880 U 4.4 U 440 U 110 U 880 U iso‐Valeric acid mg/L 5.3 5.3 U 5.3 U 5.3 U 1,060 U 5.3 U 530 U 132.5 U 1,060 U Valeric acid mg/L 5.3 5.3 U 5.3 U 5.3 U 1,060 U 5.3 U 530 U 132.5 U 1,060 U iso‐Caproic acid mg/L 5.8 5.8 U 5.8 U 5.8 U 1,160 U 5.8 U 580 U 145 U 1,160 U Caproic acid mg/L 5.8 5.8 U 5.8 U 5.8 U 1,160 U 5.8 U 580 U 145 U 1,160 U Heptanoic acid mg/L 6.6 6.6 U 6.6 U 6.6 U 1,320 U 6.6 U 660 U 165 U 1,320 U Trace Mercury (Round 4) Total Mercury ng/L 0.53 0.53 U 0.53 U 2.18 1.02 14 0.65 22 8.9 12 Methylmercury ng/L 0.05 0.05 U 0.05 U 0.05 U 1.19 0.0895 1.64 1.19 2.7
Notes: 1 ‐ units are mg/L as CaCO3 deg C ‐ degrees Celsius gal/min ‐ gallons per minute J ‐ Estimated value mg/L ‐ milligrams per liter mV ‐ millivolts ng/L ‐ nanograms per liter ORP ‐ oxidation‐reduction potential Q ‐ Laboratory qualifier su ‐ standard units U ‐ Below detection limit (reporting limit shown) µg/L ‐ micrograms per liter µS/cm ‐ microSiemens per centimeter
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table 3‐2 Analytical Results Round 5 ‐ September 4, 2013
Base Reporting Location Limit Field Blank Method Blank Adit 05‐09 ChitRem Pre 05‐07 SAPS Pre 05‐08 BCR1 05‐01 BCR2 05‐02 BCR3 05‐03 BCR4 05‐04 BCR5 05‐05 BCR6 05‐06 Total/Dissolved TDTDTD T D T D T DTDTDT DTDTD Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.105 0.105 U 0.095 U 0.105 U 12.6 12.4 0.105 U 0.095 U 2.42 12.4 1.72 1.55 0.105 U 0.095 U 0.105 U 0.095 U 0.105 U 0.095 U 0.105 U 0.095 U 0.105 U 0.095 U Antimony mg/L 0.106 0.106 U 0.095 U 0.106 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.04 0.04 U 0.036 U 0.04 U 0.051 0.039 0.04 U 0.036 U 0.04 U 0.039 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 0.045 Barium mg/L 0.017 0.017 U 0.517 0.017 U 0.017 U 0.108 U 0.097 0.652 J+ 0.056 0.243 U 0.144 0.13 U 0.206 0.562 J+ 0.157 0.132 U 0.21 0.382 U 0.146 0.659 J+ 0.359 0.755 J+ Cadmium mg/L 0.003 0.003 U 0.002 U 0.003 U 0.136 0.141 0.003 U 0.002 U 0.025 0.142 0.032 0.029 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U Calcium mg/L 0.285 0.285 U 0.257 U 0.285 U 106 102 212 208 186 102 201 181 703 766 242 238 764 603 303 286 943 924 Chromium mg/L 0.024 0.024 U 0.022 U 0.024 U 0.155 0.113 0.024 U 0.022 U 0.127 0.112 0.085 0.077 0.024 U 0.022 U 0.026 0.027 0.024 U 0.022 U 0.024 U 0.022 U 0.024 U 0.022 U Cobalt mg/L 0.011 0.011 U 0.01 U 0.011 U 0.013 0.019 0.011 U 0.01 U 0.013 0.019 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U Copper mg/L 0.008 0.008 U 0.007 U 0.008 U 3.57 3.8 0.012 0.008 0.187 3.83 0.108 0.098 0.008 0.007 U 0.03 0.007 U 0.008 U 0.007 U 0.067 0.007 U 0.008 U 0.007 U Iron mg/L 0.117 0.122 0.111 0.119 158 150 13.3 10.4 131 150 97.3 87.6 6.97 0.517 33.7 31.6 4.94 2.75 2.58 0.173 2.53 1.16 Lead mg/L 0.019 0.019 U 0.017 U 0.019 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.011 0.011 U 0.017 0.011 U 24.8 25.3 30.5 28.5 26.5 25.4 30 27 47.9 48.7 30.2 28 55.9 44.5 36 33 80.2 76.1 Manganese mg/L 0.016 0.016 U 0.014 U 0.016 U 2.09 2.11 1.44 1.37 2.39 2.1 2.67 2.404 0.668 0.648 2.81 2.74 1.56 1.64 1.34 1.2 0.735 0.679 Mercury mg/L 0.139 NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Nickel mg/L 0.005 0.005 U 0.004 U 0.005 U 0.033 0.033 0.005 U 0.004 U 0.037 0.033 0.02 0.018 0.006 0.006 0.005 U 0.004 U 0.007 0.005 0.006 0.004 0.016 0.014 Potassium mg/L 0.945 0.945 U 0.852 U 0.945 U 2.03 2.47 3.13 3.6 2.5 2.53 3.51 3.16 6.67 7.15 3.57 3.91 10.6 7.64 8.1 7.83 17.4 17 Silver mg/L 0.003 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U Sodium mg/L 1.52 1.52 U 1.71 3.82 9.81 13.1 12.7 14.7 9.8 13 13.8 12.4 23.2 26.4 9.94 11.8 15.1 15.7 19.2 20.6 37.6 37.2 Vanadium mg/L 0.029 0.029 U 0.026 U 0.029 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U Zinc mg/L 0.006 0.007 0.305 0.015 64.1 61.5 0.026 J+ 0.3113 J+ 57.3 65.1 28.7 26.1 0.035 J+ 0.241 U 2.58 0.667 J+ 0.09 J+ 0.26 U 0.519 0.307 U 0.034 J+ 0.22 U General Chemistry Alkalinity, Total1 mg/L 5 63 NR 5 U 1,310 63 125 3,440 250 2,880 1,630 6,000 pH SU NA 5.55 NR 3.36 6.44 5.08 5.67 6.54 6.3 6.47 6.68 6.52 Sulfide mg/L 0.01 0.01 U NR NR NR NR 0.01 U 1 0.16 200 125 11 Chloride mg/L 1.14 0.11 U 0.114 U 3.75 3.91 3.59 4.04 5.1 3.14 1.54 7.29 7.03 Fluoride mg/L 0.22 0.031 0.022 U 2.07 1.08 2.07 1.58 0.22 U 1.2 0.22 U 0.64 0.22 U Sulfate mg/L 3.31 0.33 U 0.331 U 2,004 38.5 1,003 1,400 3.31 U 610 222 30.3 3.31 U Volatile Fatty Acids Acetic acid mg/L 3 3 U 3 U 3 U 2,044 3 U 1,740 27.1 3,717 Propionic acid mg/L 3.9 3.9 U 3.9 U 3.9 U 177 3.9 U 141 63.1 352 iso‐Butyric acid mg/L 4.4 4.4 U 4.4 U 4.4 U 44 U 4.4 U 48.9 29 213 Butyric acid mg/L 4.4 4.4 U 4.4 U 4.4 U 188 4.4 U 139 36.8 827 iso‐Valeric acid mg/L 5.3 5.3 U 5.3 U 5.3 U 53 U 5.3 U 88.3 45.2 418 Valeric acid mg/L 5.3 5.3 U 5.3 U 5.3 U 53 U 5.3 U 53 U 11.9 193 iso‐Caproic acid mg/L 5.8 5.8 U 5.8 U 5.8 U 58 U 5.8 U 58 U 5.8 U 58 U Caproic acid mg/L 5.8 5.8 U 5.8 U 5.8 U 58 U 5.8 U 58 U 5.8 U 73.5 Heptanoic acid mg/L 6.6 6.6 U 6.6 U 6.6 U 66 U 6.6 U 66 U 6.6 U 66 U
Notes: 1 ‐ units are mg/L as CaCO3
deg C ‐ degrees Celsius gal/min ‐ gallons per minute J ‐ Estimated value mg/L ‐ milligrams per liter mV ‐ millivolts ORP ‐ oxidation‐reduction potential Q ‐ Laboratory qualifier su ‐ standard units U ‐ Below detection limit (reporting limit shown) µg/L ‐ micrograms per liter µS/cm ‐ microSiemens per centimeter
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table 3‐3 Sulfate Reduction Lab Sample Conductivity Sample Name Date Temp (oC) pH (su) ORP (mV) DO (mg/L) ID (uS/cm) BCR1 01‐01 7/10/2013 21.04 6.25 3928 ‐158.5 0.11 BCR1 02‐01 7/23/2013 18.75 5.42 1484 5.6 0.7 BCR1 03‐01 8/6/2013 18.63 5.38 1395 ‐16.6 0.86 BCR1 04‐01 8/20/2013 16.56 5.9 1215 ‐21.4 1.91 BCR1 05‐01 9/4/2013 15.49 5.62 1196 53.5 0.42
BCR2 01‐02 7/10/2013 21.63 6.64 35860 ‐195.4 0.29 BCR2 02‐02 7/23/2013 18.24 6.54 20550 ‐162.9 0.48 BCR2 03‐02 8/6/2013 18.16 6.44 8045 ‐162.9 0.82 BCR2 04‐02 8/20/2013 16.17 6.36 8795 ‐294.4 1.52 BCR2 05‐02 9/4/2013 15.09 6.34 4367 ‐181 0.27
BCR3 01‐03 7/10/2013 20.83 6.41 7404 149.5 0.13 BCR3 02‐03 7/23/2013 19.36 5.99 1448 ‐118.8 0.37 BCR3 03‐03 8/6/2013 18.81 6.04 1407 ‐32.1 0.67 BCR3 04‐03 8/20/2013 16.36 6.16 1286 ‐209.4 1.16 BCR3 05‐03 9/4/2013 15.33 6.26 1237 ‐171.2 0.32
BCR4 01‐04 7/10/2013 21.21 6.7 23850 ‐178.9 0.17 BCR4 02‐04 7/23/2013 20.23 6.59 14510 ‐162.9 0.33 BCR4 03‐04 8/6/2013 17.98 6.26 9600 ‐167.6 0.9 BCR4 04‐04 8/20/2013 16.04 6.25 2076 ‐247.6 1.51 BCR4 05‐04 9/4/2013 15.14 6.31 2943 ‐236.6 0.16
BCR5 01‐05 7/10/2013 21.53 6.51 14800 ‐158.1 0.06 BCR5 02‐05 7/23/2013 19.66 6.64 4790 ‐299 0.35 BCR5 03‐05 8/6/2013 19.18 6.19 2766 ‐216.4 0.56 BCR5 04‐05 8/20/2013 16.4 6.43 2833 ‐339.5 0.93 BCR5 05‐05 9/4/2013 15.42 6.62 2087 ‐231.3 0.08
BCR6 01‐06 7/10/2013 21.81 6.69 37260 ‐178.5 0.2 BCR6 02‐06 7/23/2013 19.02 6.41 12030 ‐284.7 0.34 BCR6 03‐06 8/6/2013 18.48 6.3 13770 ‐192.9 0.74 BCR6 04‐06 8/20/2013 15.34 6.34 9983 ‐311.4 1.86 BCR6 05‐06 9/4/2013 16.21 6.32 4551 ‐207.9 0.38
ChitRem 01‐07 7/10/2013 24.78 7.02 7130 ‐155.4 0.07 ChitRem 02‐07 7/23/2013 19.76 6.58 4092 ‐321.2 0.28 ChitRem 03‐07 8/6/2013 19.42 5.94 3037 ‐215.5 0.74 ChitRem 04‐07 8/20/2013 16.57 6.05 2802 ‐162.7 1.08 ChitRem 05‐07 9/4/2013 16.08 6.32 1824 ‐202.5 0.16
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 2 Table 3‐3 Sulfate Reduction Lab Sample Conductivity Sample Name Date Temp (oC) pH (su) ORP (mV) DO (mg/L) ID (uS/cm) SAPS 01‐08 7/10/2013 22.98 6.22 1763 ‐132.6 0.12 SAPS 02‐08 7/23/2013 19.47 5.89 1509 ‐143 0.78 SAPS 03‐08 8/6/2013 19.31 5.85 1465 ‐84.7 0.9 SAPS 04‐08 8/20/2013 16.27 5.85 1447 ‐31.3 1.14 SAPS 05‐08 9/4/2013 15.17 6.02 1387 27.5 0.54
Adit 01‐09 7/10/2013 13.17 3.34 1470 389.1 2.04 Adit 02‐09 7/23/2013 10.71 3.14 1541 397.6 1.59 Adit 03‐09 8/6/2013 10.94 3.07 1513 403.8 1.88 Adit 04‐09 8/20/2013 10.13 3.26 1532 320.9 1.1 Adit 05‐09 9/4/2013 11.08 3.37 1366 357.3 0.05
Notes: oC ‐ degree Celsius DO ‐ dissolved oxygen ID ‐ identification mg/L ‐ milligram per liter mV ‐ millivolt ORP ‐ oxidation reduction potential µS/cm ‐ micro Siemens per centimeter
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 2 of 2 Table 3‐4 Dissolved Metals Removal Efficiency
Dissolved Metals Data 7/10/2013 Ag Al As Ba Ca Cd Co Cr Cu Fe K 1st Event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 101‐01 NA 99% NA ‐381% ‐140% 100% 28% > 90% 99% 91% ‐23286% BCR2 01‐02 NA 70% ‐4039% < ‐2973% ‐3354% 92% ‐971% 86% 97% 91% ‐31187% BCR 301‐03 NA 98% NA ‐1535% ‐288% 100% 19% 93% 100% 98% ‐45498% BCR 401‐04 NA 78% ‐2408% < ‐2251% ‐2447% 97% ‐558% 90% 99% 94% ‐33218% BCR 501‐05 NA 91% ‐51% < ‐2345% ‐1031% 99% > ‐7% 93% 100% 98% ‐54076% BCR 601‐06 NA 66% ‐4067% < ‐3298% ‐3721% 87% ‐1236% 83% 96% 87% ‐42202%
Dissolved Metals Data 7/23/2013 Ag Al As Ba Ca Cd Co Cr Cu Fe K 2nd Event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 102‐01 NA 96% NA 8% ‐68% 99% > 11% > 51% 97% 49% ‐121% BCR2 02‐02 ‐7% < 89% NA ‐255% ‐1266% 99% > 11% > 92% > 100% > 100% ‐480% BCR 302‐03 NA 99% NA ‐33% ‐110% 99% > 11% > 83% 99% 83% ‐132% BCR 402‐04 ‐23% < 94% NA ‐196% ‐715% 99% > 11% > 92% > 100% > 97% ‐459% BCR 502‐05 ‐93% < 98% NA ‐198% ‐297% 99% > 11% > 92% > 100% > 100% ‐325% BCR 602‐06 3% < 92% NA ‐251% ‐989% 99% > 11% > 92% > 100% > 100% ‐662%
Dissolved Metals Data 8/6/2013 Ag Al As Ba Ca Cd Co Cr Cu Fe K 3rd Event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 103‐01 NA 92% NA ‐530% ‐72% 90% 16% 19% 95% 19% ‐130% BCR2 03‐02 NA 86% NA ‐1451% ‐1248% 99% > 40% > 91% > 100% > 100% ‐650% BCR 303‐03 NA 98% NA ‐937% ‐106% 99% > 40% > 57% 97% 56% ‐328% BCR 403‐04 NA 89% ‐2% < ‐1677% ‐1049% 99% > 40% > 91% > 100% > 99% ‐1798% BCR 503‐05 NA 97% NA ‐949% ‐358% 99% > 40% > 91% > 100% > 100% ‐508% BCR 603‐06 NA 82% ‐98% < ‐3593% ‐1683% 99% > 40% > 91% > 100% > 100% ‐2059%
Dissolved Metals Data 8/20/2013 Ag Al As Ba Ca Cd Co Cr Cu Fe K 4th Event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 104‐01 NA 96% NA 8% ‐68% 99% > 11% > 51% 97% 49% ‐121% BCR2 04‐02 ‐0.1 < 89% NA ‐255% ‐1266% 99% > 11% > 92% > 100% > 100% ‐480% BCR 304‐03 NA 99% NA ‐33% ‐110% 99% > 11% > 83% 99% 83% ‐132% BCR 404‐04 ‐0.2 < 94% NA ‐196% ‐715% 99% > 11% > 92% > 100% > 97% ‐459% BCR 504‐05 ‐0.9 < 98% NA ‐198% ‐297% 99% > 11% > 92% > 100% > 100% ‐325% BCR 604‐06 0.0 < 92% NA ‐251% ‐989% 99% > 11% > 92% > 100% > 100% ‐662%
Dissolved Metals Data 9/3/2013 Ag Al As Ba Ca Cd Co Cr Cu Fe K 5th event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 105‐01 NA 88% 7% > 26% ‐77% 80% 9% 32% 97% 42% ‐26% BCR2 05‐02 NA 99% > 7% > ‐220% ‐651% 99% > 48% > 80% > 100% > 100% ‐186% BCR 305‐03 NA 99% > 7% > 25% ‐133% 99% > 48% > 76% 100% > 79% ‐56% BCR 405‐04 NA 99% > 7% > ‐118% ‐491% 99% > 48% > 80% > 100% > 98% ‐206% BCR 505‐05 NA 99% > 7% > ‐276% ‐180% 99% > 48% > 80% > 100% > 100% ‐213% BCR 605‐06 NA 99% > ‐16% ‐330% ‐806% 99% > 48% > 80% > 100% > 99% ‐580%
Notes: NA ‐ when both the influent and effluent concentrations were below the reporting limits RL ‐ reporting limit, information in this column is related to sample reporting limit < ‐ when the influent concentration is non‐detect (less than the reporting limit) but the effluent concentration is reported > ‐ When the influent concentration is reported, but the effluent concentration is non‐detect (less than the reporting limit)
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 2 Table 3-4 Dissolved Metals Removal Efficiency Dissolved Metals Data 7/10/2013 Mg Mn Na Ni Pb Sb V Zn 1st Event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 101‐01 ‐438% ‐41% ‐1108% 71% NA NA NA 100% BCR2 01‐02 ‐3812% ‐4% ‐28383% ‐544% NA NA NA 99% BCR 301‐03 ‐1011% ‐44% ‐2450% 28% NA NA NA 100% BCR 401‐04 ‐3081% 25% ‐19303% ‐315% NA NA NA 100% BCR 501‐05 ‐2028% ‐94% ‐4477% ‐6% NA NA NA 100% BCR 601‐06 ‐4695% ‐13% ‐33482% ‐718% NA NA ‐48% < 99%
Dissolved Metals Data 7/23/2013 Mg Mn Na Ni Pb Sb V Zn 2nd Event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 102‐01 ‐1% 2% NA 85% > 53% > NA NA 79% BCR2 02‐02 ‐302% 67% ‐316% 71% 53% > NA NA 100% BCR 302‐03 ‐3% ‐13% 0% 85% > 53% > NA NA 99% BCR 402‐04 ‐118% 7% ‐57% 85% > 53% > NA NA 100% BCR 502‐05 ‐58% 36% ‐100% 85% > 53% > NA NA 100% BCR 602‐06 ‐255% 69% ‐319% 59% > 53% > NA NA 100%
Dissolved Metals Data 8/6/2013 Mg Mn Na Ni Pb Sb V Zn 3rd Event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 103‐01 ‐5% ‐15% ‐3% 50% 58% > NA NA 59% BCR2 03‐02 ‐200% 77% ‐192% 76% 58% > NA NA 100% BCR 303‐03 ‐12% ‐45% ‐5% 91% > 58% > NA NA 100% BCR 403‐04 ‐221% 26% ‐352% 70% 58% > NA NA 100% > BCR 503‐05 ‐72% 26% ‐109% 91% > 58% > NA NA 100% BCR 603‐06 ‐464% 57% ‐1037% 44% 58% > NA NA 100% >
Dissolved Metals Data 8/20/2013 Mg Mn Na Ni Pb Sb V Zn 4th Event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 104‐01 ‐1% 2% 0% 85% > 53% > NA NA 79% BCR2 04‐02 ‐302% 67% ‐316% 71% 53% > NA NA 100% BCR 304‐03 ‐3% ‐13% 0% 85% > 53% > NA NA 99% BCR 404‐04 ‐118% 7% ‐57% 85% > 53% > NA NA 100% BCR 504‐05 ‐58% 36% ‐100% 85% > 53% > NA NA 100% BCR 604‐06 ‐255% 69% ‐319% 59% 53% > NA NA 100%
Dissolved Metals Data 9/3/2013 Mg Mn Na Ni Pb Sb VZn 5th event Sample Name Sample ID % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL % Removal RL BCR 105‐01 ‐7% ‐14% 5% 46% NA NA NA 59% BCR2 05‐02 ‐92% 69% ‐102% 81% NA NA NA 100% BCR 305‐03 ‐11% ‐30% 10% 88% > NA NA NA 99% BCR 405‐04 ‐76% 22% ‐20% 85% NA NA NA 100% BCR 505‐05 ‐30% 43% ‐58% 87% NA NA NA 100% BCR 605‐06 ‐201% 68% ‐185% 57% NA NA NA 100%
Notes: NA ‐ when both the influent and effluent concentrations were below the reporting limits RL ‐ reporting limit, information in this column is related to sample reporting limit < ‐ when the influent concentration is non‐detect (less than the reporting limit) but the effluent concentration is reported > ‐ When the influent concentration is reported, but the effluent concentration is non‐detect (less than the reporting limit)
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 2 of 2 Table 3‐5 Sulfate Reduction Sulfate Sulfide Overall Sulfate (as SO4) Sulfate Reduction Reduction Location Date Result Q Result Q 7/10/2013 1765 NS NA NA 7/23/2013 1893 NS NA NA Adit 8/6/2013 1840 NS NA NA 8/20/2013 2180 NS NA NA 9/4/2013 2004 NS NA NA 7/10/2013 719.4 59% 59% 7/23/2013 987 0.52 48% 48% BCR1 8/6/2013 1001 0.01 46% 46% 8/20/2013 670 0.01 U 69% 69% 9/4/2013 1400 0.01 U 30% 30% 7/10/2013 1367 23% 23% 7/23/2013 180 7.72 90% 90% BCR2 8/6/2013 495 1.70 73% 73% 8/20/2013 118 1.5 95% 95% 9/4/2013 3.3 U 0.7 100% 100% 7/10/2013 802 NS 55% NA 7/23/2013 821 NS 57% NA SAPS Pre‐ 8/6/2013 809 NS 56% NA Treatment 8/20/2013 916 NS 58% NA 9/4/2013 1003 NS 50% NA 7/10/2013 421 47% 76% 7/23/2013 547 7.10 33% 71% BCR3 8/6/2013 611 0.50 24% 67% 8/20/2013 440 0.08 52% 80% 9/4/2013 610 0.16 39% 70% 7/10/2013 948 ‐18% 46% 7/23/2013 97 3.36 88% 95% BCR4 8/6/2013 133 6.30 84% 93% 8/20/2013 120 1.9 87% 94% 9/4/2013 222 200 78% 89% 7/10/2013 679 NS 62% NA 7/23/2013 541 NS 71% NA ChitRem Pre‐ 8/6/2013 424 NS 77% NA Treatment 8/20/2013 114 NS 95% NA 9/4/2013 38 NS 98% NA
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 2 Table 3‐5 Sulfate Reduction Sulfate Sulfide Overall Sulfate (as SO4) Sulfate Reduction Reduction Location Date Result Q Result Q 7/10/2013 344 49% 80% 7/23/2013 288 60.0 47% 85% BCR5 8/6/2013 312 24.0 26% 83% 8/20/2013 32 20 72% 99% 9/4/2013 30 125 21% 98% 7/10/2013 1284 ‐89% 27% 7/23/2013 67 11.0 88% 96% BCR6 8/6/2013 45 10.0 89% 98% 8/20/2013 34.0 97% 100% 9/4/2013 3.31 U 11.0 91% 100%
Notes: All results in units of mg/L All results shown are normal field samples (no field duplicates)
NA ‐ not applicable NS ‐ not sampled Q ‐ qualifier U ‐ non‐detect
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 2 of 2
Figures
3370 3368 3360 3366 3364 3362 3358 3360 3358 3356 3356 3354 Legend 3354 3352 3350 3352 A! Sample Location 3350 3348 Adit Water Diversion System 3346 Adit water collection pipe 2-foot Contours 3344 connected to adit opening 3342
3340 Roads
3338 Formosa A
! 3336 1 Adit Combined feed tank and header tank
3334 overflows to adit water diversion system
3332
3330 3328 3326 Existing manhole 3324 Feed tank (not used) 3322 3320 3318 Header Tanks (1-3, Combined flow for discharge to 3316 from left to right) adit water diversion system 3314 3312 3310 Feed line to 3304 Existing adit water 3308 BCR barrels (no 3306 collection pond pre-treatment) 3302
SAPS pre-treatment Feed lines to BCR barrels 6'x8' shelter containing 6 BCR barrels 3300 3298 ChitoRem pre-treatment
3296 Existing concrete settling tank 3294 3292 3290 3288 3286 3284 3282 0 10 20 40 3280
3278 Feet
3276
3274 A
! MW-7A Existing concrete
settling tank 3272 Geographic Data Standards: ± 3270 Projected Coordinate System: NAD 1983 State Plane Oregon FIPS Zone 3602
Data Sources: Bureau of Land Management: Approximate location 2005 Topography of existing concrete block wall
3266 3264 3262 3260 3258 3256 3254 Figure 1-1 3252 3250 3248 3246 Pilot-Scale Treatability Study 3244 3242 Water Treatment System 3230 3240 3228 3238 3226 3236 3234 Formosa Mine Superfund Site 3224 3268 3232 3222 Douglas County, Oregon 3220
A B Adit Portal Overflow Line
PVC Anchor
Feed Tank Line
Figure 2‐1 HDPE pipe installation at adit portal. A: Shows HDPE pipe inlet and PVC pipe overflow configuration. B: Shows PVC anchor attached to HDPE pipe buried under adit portal dam
A B Influent Line
Operational Water Level
Effluent/TS Influent Line
Overflow Line
Figure 2‐2 Feed Tank Installation. A: View of tank outlet feeding treatability system. B: View of tank outlet used as for tank overflow and adit water inlet port with globe valve
Inverted U‐Shaped Anti‐Siphon Vent Manifold
Effluent Sampling Port
Parameter Sampling Port
Figure 2‐3 Pre‐Treatment and BCR barrel drainage manifold
Woody Substrate BCRs SAPS Pre‐Treatment
Chitorem Pre‐Treatment
Feed Tank Overflow Chitorem BCRs Head Tanks
Figure 2‐4 Configuration of treatability system
BCR2 Influent
BCR1 Influent
Split T
Timer Valve
Figure 2‐5 Configuration example of influent diversion using a timer valve between BCR 1 and BCR 2
7.5 0.8
7 0.7
6.5
0.6
6
0.5 5.5 (in)
(su)
5 0.4 pH
4.5 Precipitation 0.3
4
0.2
3.5
0.1 3
2.5 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 Date Precipitation Adit BCR1 BCR2 BCR3 BCR4 BCR5 BCR6 ChitRem SAPS
Figure 3‐1 pH Measurements Formosa Mine Pilot Study 40000 0.8
35000 0.7
30000 0.6
25000 0.5 (in)
(us/cm)
20000 0.4 Precipitation
Conductivity 15000 0.3
10000 0.2
5000 0.1
0 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 Date Precipitation Adit BCR1 BCR2 BCR3 BCR4 BCR5 BCR6 ChitRem SAPS
Figure 3‐2 Conductivity Measurements Formosa Mine Pilot Study 2.5 0.8
0.7
2
0.6
0.5 1.5 (mg/L) (in)
DO decrease in all samples after aquiring new YSI Probe 0.4 Oxygen
1 Precipitation 0.3 Dissolved
0.2
0.5
0.1
0 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 Date Precipitation Adit BCR1 BCR2 BCR3 BCR4 BCR5 BCR6 ChitRem SAPS
Figure 3‐3 Dissolved Oxygen Measurements Formosa Mine Pilot Study 500 0.8
400 0.7
300 0.6
(mV) 200
0.5 (in) 100 Potential
0.4
0 Reduction
Precipitation 0.3 ‐100 Oxidation 0.2 ‐200
0.1 ‐300
‐400 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 Date Precipitation Adit BCR1 BCR2 BCR3 BCR4 BCR5 BCR6 ChitRem SAPS
Figure 3‐4 Oxidation‐Reduction Potential Measurements Formosa Mine Pilot Study 30 0.8
0.7 25
0.6
20 0.5 C) o (in) (
15 0.4 Precipitation Temperature 0.3 10
0.2
5 0.1
0 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 Date Precipitation Adit BCR1 BCR2 BCR3 BCR4 BCR5 BCR6 ChitRem SAPS
Figure 3‐5 Temperature Measurements Formosa Mine Pilot Study 35.0
30.0
25.0 C) o
( 20.0
15.0 Temperature
10.0
5.0
0.0 7/10/2013 7/17/2013 7/24/2013 7/31/2013 8/7/2013 8/14/2013 8/21/2013 8/28/2013 9/4/2013 Date Daily Minimum Temperature Daily Maximum Temperature
Figure 3‐6 Daily Temperature Measurements Formosa Mine Pilot Study 100.0010000016 0.8 6 Green histogram represents DL: 0.095daily µg/Lprecipitation
14 0.7 5
10.00 0.6 1000012 0.6
4 0.5 10 0.5 (in)
(in) (in)
(mg/L)
(ug/L) (µg/L)
1.00 0.4 10008 0.4 3 Precipitation Aluminum Antimony 0.3 Precipitation Precipitation Aluminum 6 0.3 2
0.10 Reporting Limit = 200 ug/L 0.2 Reporting Limit: 0.095 µg/L 4100 0.2
0.1 1 2 0.1
0.01 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 0 10 0 0 7/5/201310/8/2012 7/15/2013 10/18/2012 7/25/2013 10/28/2012 8/4/2013 11/7/2012Date 8/14/2013 11/17/2012 8/24/2013 11/27/2012 9/3/2013 12/7/2012 9/13/2013 12/17/2012 DateDate PrecipitationTSPINF Adit BCR1TSPINF ND BCR2 TSP01BCR3 BCR4TSP01 ND BCR5 TSP02BCR6 ChitRemTSP02 ND SAPS PrecipitationTSP03 Adit TSP03BCR1 ND BCR2 TSP04 BCR3 BCR4TSP04 NDBCR5 BCR6TSP05 ChitRem TSP05SAPS ND
Figure 3‐7 Dissolved Aluminum Concentrations Formosa Mine Pilot Study 10000010.0016 0.8 6 Green histogram represents DL: 0.095daily µg/Lprecipitation
14 0.7 5
0.6 1000012 0.6
1.00 4 0.5 10 0.5 (in)
(in) (in)
(mg/L)
(ug/L) (µg/L)
0.4 10008 0.4 3 Arsenic Precipitation Antimony 0.3 Precipitation Precipitation Aluminum 0.106 0.3 2
Reporting Limit = 200 ug/L 0.2 4100 0.2
Reporting Limit: 0.036 mg/L 0.1 1 2 0.1
0.01 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 0 10 0 0 7/5/201310/8/2012 7/15/2013 10/18/2012 7/25/2013 10/28/2012 8/4/2013 11/7/2012Date 8/14/2013 11/17/2012 8/24/2013 11/27/2012 9/3/2013 12/7/2012 9/13/2013 12/17/2012 DateDate PrecipitationTSPINF Adit BCR1TSPINF ND BCR2 TSP01BCR3 BCR4TSP01 ND BCR5 TSP02BCR6 ChitRemTSP02 ND SAPS PrecipitationTSP03 Adit TSP03BCR1 ND BCR2 TSP04 BCR3 BCR4TSP04 NDBCR5 BCR6TSP05 ChitRem TSP05SAPS ND
Figure 3‐8 Dissolved Arsenic Concentrations Formosa Mine Pilot Study 100000161.000 0.8 6 Green histogram represents DL: 0.095daily µg/Lprecipitation
14 0.7 5
0.6 1000012 0.6
0.100 4 0.5 10 0.5 (in)
(in) (in)
(mg/L)
(ug/L) (µg/L)
0.4 10008 0.4 3 Precipitation Cadmium Antimony 0.3 Precipitation Precipitation Aluminum 0.0106 0.3 2
Reporting Limit = 200 ug/L 0.2 4100 0.2
0.1 1 2 0.1 Reporting Limit: 0.002 mg/L
0.001 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 0 10 0 0 7/5/201310/8/2012 7/15/2013 10/18/2012 7/25/2013 10/28/2012 8/4/2013 11/7/2012Date 8/14/2013 11/17/2012 8/24/2013 11/27/2012 9/3/2013 12/7/2012 9/13/2013 12/17/2012 DateDate PrecipitationTSPINF Adit BCR1TSPINF ND BCR2 TSP01BCR3 BCR4TSP01 ND BCR5 TSP02BCR6 ChitRemTSP02 ND SAPS PrecipitationTSP03 Adit TSP03BCR1 ND BCR2 TSP04 BCR3 BCR4TSP04 NDBCR5 BCR6TSP05 ChitRem TSP05SAPS ND
Figure 3‐9 Dissolved Cadmium Concentrations Formosa Mine Pilot Study 10000 0.8
0.7
1000 0.6
0.5 (in)
(mg/L) 100 0.4 Calcium Precipitation 0.3
10 0.2
Reporting Limit: 0.257 mg/L 0.1
1 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 Date Precipitation Adit BCR1 BCR2 BCR3 BCR4 BCR5 BCR6 ChitRem SAPS
Figure 3‐10 Dissolved Calcium Concentrations Formosa Mine Pilot Study 10000016 1.00 0.8 6 Green histogram represents DL: 0.095daily µg/Lprecipitation
14 0.7 5
0.6 1000012 0.6
4 0.5 10 0.5 (in)
(in) (in)
(mg/L)
(ug/L) (µg/L)
0.10 0.4 10008 0.4 3 Precipitation Chromium Antimony 0.3 Precipitation Precipitation Aluminum 6 0.3 2
Reporting Limit = 200 ug/L 0.2 4100 0.2
Reporting Limit: 0.024 mg/L 0.1 1 2 0.1
0.01 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 0 10 0 0 7/5/201310/8/2012 7/15/2013 10/18/2012 7/25/2013 10/28/2012 8/4/2013 11/7/2012Date 8/14/2013 11/17/2012 8/24/2013 11/27/2012 9/3/2013 12/7/2012 9/13/2013 12/17/2012 DateDate PrecipitationTSPINF Adit BCR1TSPINF ND BCR2 TSP01BCR3 BCR4TSP01 ND BCR5 TSP02BCR6 ChitRemTSP02 ND SAPS PrecipitationTSP03 Adit TSP03BCR1 ND BCR2 TSP04 BCR3 BCR4TSP04 NDBCR5 BCR6TSP05 ChitRem TSP05SAPS ND
Figure 3‐11 Dissolved Chromium Concentrations Formosa Mine Pilot Study 1000001610.000 0.8 6 Green histogram represents DL: 0.095daily µg/Lprecipitation
14 0.7 5
1.000 0.6 1000012 0.6
4 0.5 10 0.5 (in)
(in) (in)
(mg/L)
(ug/L) (µg/L)
0.100 0.4 10008 0.4 3 Copper Precipitation Antimony 0.3 Precipitation Precipitation Aluminum 6 0.3 2
0.010 Reporting Limit = 200 ug/L 0.2 4100 0.2 Reporting Limit: 0.007 mg/L 0.1 1 2 0.1
0.001 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 0 10 0 0 7/5/201310/8/2012 7/15/2013 10/18/2012 7/25/2013 10/28/2012 8/4/2013 11/7/2012Date 8/14/2013 11/17/2012 8/24/2013 11/27/2012 9/3/2013 12/7/2012 9/13/2013 12/17/2012 DateDate PrecipitationTSPINF Adit BCR1TSPINF ND BCR2 TSP01BCR3 BCR4TSP01 ND BCR5 TSP02BCR6 ChitRemTSP02 ND SAPS PrecipitationTSP03 Adit TSP03BCR1 ND BCR2 TSP04 BCR3 BCR4TSP04 NDBCR5 BCR6TSP05 ChitRem TSP05SAPS ND
Figure 3‐12 Dissolved Copper Concentrations Formosa Mine Pilot Study 100000161000.0 0.80.8 6 Green histogram represents DL: 0.095daily µg/Lprecipitation
14 0.70.7 5
100.0 0.6 1000012 0.6
4 0.5 10 0.5 (in)
(in) (in)
(ug/L) (µg/L)
(mg/L) 10.0 0.4 10008 0.4 3 Iron Precipitation Antimony 0.3 Precipitation Precipitation Aluminum 6 0.3 2
1.0 Reporting Limit = 200 ug/L 0.2 4100 0.2
0.1 1 2 0.1 Reporting Limit: 0.105 mg/L 0.1 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 0 10 0 0 7/5/201310/8/2012 7/15/2013 10/18/2012 7/25/2013 10/28/2012 8/4/2013 11/7/2012Date 8/14/2013 11/17/2012 8/24/2013 11/27/2012 9/3/2013 12/7/2012 9/13/2013 12/17/2012 DateDate PrecipitationTSPINF Adit BCR1TSPINF ND BCR2 TSP01BCR3 BCR4TSP01 ND BCR5 TSP02BCR6 ChitRemTSP02 ND SAPS PrecipitationTSP03 Adit TSP03BCR1 ND BCR2 TSP04 BCR3 BCR4TSP04 NDBCR5 BCR6TSP05 ChitRem TSP05SAPS ND
Figure 3‐13 Dissolved Iron Concentrations Formosa Mine Pilot Study 10000010.016 0.80.8 6 Green histogram represents DL: 0.095daily µg/Lprecipitation
14 0.70.7 5
0.6 1000012 0.6
4 0.5 10 0.5 (in)
(in) (mg/L) (in)
(ug/L) (µg/L)
1.0 0.4 10008 0.4 3 Precipitation Manganese Antimony 0.3 Precipitation Precipitation Aluminum 6 0.3 2
Reporting Limit = 200 ug/L 0.2 4100 0.2
0.1 1
2 Reporting Limit: 0.014 mg/L 0.1
0.1 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 0 10 0 0 7/5/201310/8/2012 7/15/2013 10/18/2012 7/25/2013 10/28/2012 8/4/2013 11/7/2012Date 8/14/2013 11/17/2012 8/24/2013 11/27/2012 9/3/2013 12/7/2012 9/13/2013 12/17/2012 DateDate PrecipitationTSPINF Adit BCR1TSPINF ND BCR2 TSP01BCR3 BCR4TSP01 ND BCR5 TSP02BCR6 ChitRemTSP02 ND SAPS PrecipitationTSP03 Adit TSP03BCR1 ND BCR2 TSP04 BCR3 BCR4TSP04 NDBCR5 BCR6TSP05 ChitRem TSP05SAPS ND
Figure 3‐14 Dissolved Manganese Concentrations Formosa Mine Pilot Study 1000001.00016 0.80.8 6 Green histogram represents DL: 0.095daily µg/Lprecipitation
14 0.70.7 5
0.6 1000012 0.6
0.100 4 0.5 10 0.5 (in)
(in) (in)
(mg/L) (ug/L) (µg/L)
0.4 10008 0.4 3 Nickel Precipitation Antimony 0.3 Precipitation Precipitation Aluminum 0.0106 0.3 2
Reporting Limit = 200 ug/L 0.2 4100 0.2
Reporting Limit: 0.004 mg/L 0.1 1 2 0.1
0.001 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 0 10 0 0 7/5/201310/8/2012 7/15/2013 10/18/2012 7/25/2013 10/28/2012 8/4/2013 11/7/2012Date 8/14/2013 11/17/2012 8/24/2013 11/27/2012 9/3/2013 12/7/2012 9/13/2013 12/17/2012 DateDate PrecipitationTSPINF Adit BCR1TSPINF ND BCR2 TSP01BCR3 BCR4TSP01 ND BCR5 TSP02BCR6 ChitRemTSP02 ND SAPS PrecipitationTSP03 Adit TSP03BCR1 ND BCR2 TSP04 BCR3 BCR4TSP04 NDBCR5 BCR6TSP05 ChitRem TSP05SAPS ND
Figure 3‐15 Dissolved Nickel Concentration Formosa Mine Pilot Study 100.00010000016 0.80.8 6 Green histogram represents DL: 0.095daily µg/Lprecipitation
14 0.70.7 5 10.000 0.6 1000012 0.6
4 0.5 1.00010 0.5 (in)
(in) (in)
(ug/L) (µg/L)
(mg/L) 0.4 10008 0.4 3 Zinc
0.100 Precipitation Antimony 0.3 Precipitation Precipitation Aluminum 6 0.3 2
Reporting Limit = 200 ug/L 0.2 0.0104100 0.2
0.1 1 Reporting Limit: 0.005 mg/L 2 0.1
0.001 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013 0 10 0 0 7/5/201310/8/2012 7/15/2013 10/18/2012 7/25/2013 10/28/2012 8/4/2013 11/7/2012Date 8/14/2013 11/17/2012 8/24/2013 11/27/2012 9/3/2013 12/7/2012 9/13/2013 12/17/2012 DateDate PrecipitationTSPINF Adit BCR1TSPINF ND BCR2 TSP01BCR3 BCR4TSP01 ND BCR5 TSP02BCR6 ChitRemTSP02 ND SAPS PrecipitationTSP03 Adit TSP03BCR1 ND BCR2 TSP04 BCR3 BCR4TSP04 NDBCR5 BCR6TSP05 ChitRem TSP05SAPS ND
Figure 3‐16 Dissolved Zinc Concentrations Formosa Mine Pilot Study 100000 1.4
1.2
10000
1
1000 CaCO3
0.8 (in) of mg/L
0.6
100 Precipitation Alkalinity
0.4
10
Reporting Limit: 5 mg/L 0.2
1 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013
Precipitation Adit BCR1 BCR2 BCR3 BCR4 BCR5 BCR6 ChitRem SAPS
Figure 3‐17 Total Alkalinity (as CaCO3) Concentrations Formosa Mine Pilot Study 10000 1.4
1.2
1000 1
0.8 (in)
(mg/L)
100
0.6 Sulfate Precipitation
0.4 10
Reporting Limit: 3.3 mg/L 0.2
1 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013
Precipitation Adit BCR1 BCR2 BCR3 BCR4 BCR5 BCR6 ChitRem SAPS
Figure 3‐18 Sulfate (as SO4) Concentrations Formosa Mine Pilot Study 1000.000 1.4
1.2 100.000
1 10.000
0.8 (in)
(mg/L)
1.000
0.6 Sulfide Precipitation
0.100 0.4
Reporting Limit: 0.01 mg/L 0.010 0.2
0.001 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013
Precipitation BCR1 BCR2 BCR3 BCR4 BCR5 BCR6
Figure 3‐19 Sulfide Concentrations Formosa Mine Pilot Study 100000 1.4
1.2
10000
1
1000
0.8 (in)
(mg/L)
Acetic 0.6
100 Precipitation
0.4
10
0.2
1 0 7/5/2013 7/15/2013 7/25/2013 8/4/2013 8/14/2013 8/24/2013 9/3/2013 9/13/2013
Precipitation BCR1 BCR2 BCR3 BCR4 BCR5 BCR6
Figure 3‐20 Acetic Acid Concentrations Formosa Mine Pilot Study 25
20
15 ng/L
THg MeHg Mercury,
10
5
0 Adit BCR 1BCR 2BCR 3BCR 4BCR 5BCR 6 Figure 3‐21 Trace Mercury (Round 4) Formosa Mine Pilot Study
Appendix A ChitoRem® Sediment Core Permeability Testing
U.S. SIEVE OPENING IN INCHES U.S. SIEVE NUMBERS HYDROMETER 4 2 1 1/2 3 6 10 16 30 50 100 200 6 3 1.5 3/4 3/8 4 8 14 20 40 60 140 100 95
90
85
80
75
70
65
60
55
50
45
PERCENT FINER BY WEIGHT 40
35
30
25
20
15
10
5 0 100 10 1 0.1 0.01 0.001 GRAIN SIZE IN MILLIMETERS GRAVEL SAND COBBLES SILT OR CLAY coarsefine coarse medium fine
Specimen Identification Classification Cc Cu BCR-2 POORLY GRADED SAND with GRAVEL(SP) 0.68 6.37 BCR-4 POORLY GRADED SAND with GRAVEL(SP) 0.73 5.46 BCR-6 POORLY GRADED SAND with GRAVEL(SP) 0.39 11.32 CH-PRETREAT POORLY GRADEDSAND with SILT and GRAVEL (SP-SM) 0.73 7.12
Specimen IdentificationD60 D30 D10 %Gravel %Sand %Fines BCR-2 1.09 0.36 0.17 21.3 74.2 4.5 BCR-4 1.00 0.37 0.18 22.3 73.4 4.3 BCR-6 2.45 0.45 0.22 32.9 63.7 3.4 CH-PRETREAT 1.07 0.34 0.15 24.3 69.3 6.4
GRAIN SIZE DISTRIBUTION EPA Region 10 Formosa Mine Douglas County, Oregon
Project No: 97290 Figure: 1 GSA_SPEC_ID_1COL FORMOSA LAB DATA.GPJ GINT STD US LAB.GDT 10/16/13 REV. LAB.GDT US STD GINT LAB DATA.GPJ FORMOSA GSA_SPEC_ID_1COL Sample Number: BCR-2 Sample Location: N/A Test Specifications Depth (ft): N/A B-Value (%): 100 + Lab I.D. Number: BCR-2 Consolidation stress (psi): 0.0 Sample Description: SAND with gravel Cell pressure (psi): 9.9 Test Type: Constant Head Head pressure (psi): 9.9 Tail pressure (psi): 9.5 Sample Characteristics Pressure Difference (psi) 0.36 Length of specimen (in): 5.83 Head (in) 10.1 Diameter of specimen (in): 2.43 Gradient (in/in) 1.7 Dry Density (pcf): 68.6 Specific gravity 2.56 Void Ratio: 1.33
Initial moisture content Final moisture content Wt. of wet soil & tin (g) Wt. of wet soil & tin (g) 745.62 Wt. of dry soil & tin (g) Wt. of dry soil & tin (g) 616.52 Wt. of water (g) Wt. of water (g) 129.10 Wt. of tin (g) Wt. of tin (g) 175.57 Wt. of dry soil (g) 485.62 Wt. of dry soil (g) 440.95 Moisture content (%) 37.60 Moisture content (%) 29.28
Elaps. Elaps. Direct Burette Rds B-Value Calculation: Permeability Date Time time time Head Tail Initial Final (cm/sec) (min) (sec) (cc) (cc) Trial 1 10/2/13 12:29:09 PM 0.0 0 93.6 207.6 10/2/13 12:31:09 PM 2.0 120 99.0 196.8 1.2E-03 10/2/13 12:32:09 PM 3.0 180 104.4 192.0 1.6E-03 10/2/13 12:33:09 PM 4.0 240 109.8 187.2 1.6E-03 10/2/13 12:34:09 PM 5.0 300 115.2 181.2 1.8E-03 B-value test indicated that a leak developed between the cell 10/2/13 12:35:09 PM 6.0 360 120.6 176.4 1.6E-03 water and the pore water. Pressure quickly equalized (i.e. 10/2/13 12:36:09 PM 7.0 420 124.2 171.6 1.3E-03 effective stress of zero). 10/2/13 12:37:09 PM 8.0 480 129.6 165.6 1.8E-03 10/2/13 12:38:09 PM 9.0 540 135.0 159.6 1.8E-03 10/2/13 12:39:09 PM 10.0 600 140.4 154.8 1.7E-03
1.0E‐02 (cm/sec)
Permeability
1.0E‐03 0 100 200 300 400 500 600 700
Elapsed Time (sec) Notes: Initial moisture content back-calculated from final dry weight k = 1.8E-03 cm/sec
Permeability Test Results FIGURE Formosa Mine Douglas County, Oregon Project NumberTested By Test Date Reviewed By Review Date 2 97290 MAL 10/2/2013
BCR-2 Permeability.xlsx Sample Number: BCR-4 Sample Location: N/A Test Specifications Depth (ft): N/A B-Value (%): 80.4% Lab I.D. Number: BCR-4 Consolidation stress (psi): 3.2 Sample Description: SAND with gravel Cell pressure (psi): 79.0 Test Type: Constant Head Head pressure (psi): 75.8 Tail pressure (psi): 75.1 Sample Characteristics Pressure Difference (psi) 0.67 Length of specimen (in): 5.99 Head (in) 18.6 Diameter of specimen (in): 2.35 Gradient (in/in) 3.1 Dry Density (pcf): 71.7 Specific gravity 2.52 Void Ratio: 1.19
Initial moisture content Final moisture content Wt. of wet soil & tin (g)N/A Wt. of wet soil & tin (g) 847.61 Wt. of dry soil & tin (g)N/A Wt. of dry soil & tin (g) 666.47 Wt. of water (g) N/A Wt. of water (g) 181.14 Wt. of tin (g) N/A Wt. of tin (g) 209.55 Wt. of dry soil (g) 507.37 Wt. of dry soil (g) 456.92 Moisture content (%)32.80 Moisture content (%) 39.64
Elaps. Elaps. Direct Burette Rds B-Value Calculation: Permeability Date Time time time Head Tail Initial Final (cm/sec) (min) (sec) (cc) (cc) Trial 17 10/9/13 8:09:00 AM 0.0 0 215.9 249.3 Cell Pressure 60.3 65.0 10/9/13 8:19:00 AM 10.0 600 264.5 200.3 8.4E-04 Pore Pressure 57.1 60.6 10/9/13 8:24:00 AM 15.0 900 288.0 177.6 7.9E-04 B-value 74.5% 10/9/13 8:29:00 AM 20.0 1200 308.7 157.2 7.4E-04 Trial 18 10/9/13 8:34:00 AM 25.0 1500 333.0 131.4 9.0E-04 Cell Pressure 65.0 69.9 10/9/13 8:39:00 AM 30.0 1800 357.3 106.2 9.3E-04 Pore Pressure 61.8 65.7 10/9/13 8:44:00 AM 35.0 2100 382.5 76.8 1.0E-03 B-value 79.6% 10/9/13 8:49:00 AM 40.0 2400 409.5 52.8 9.6E-04 Trial 19 10/9/13 8:54:00 AM 45.0 2700 433.8 29.4 1.0E-03 Cell Pressure 69.9 74.5 Pore Pressure 66.5 70.2 B-value 80.4%
1.0E‐02 (cm/sec)
1.0E‐03 Permeability
1.0E‐04 0 500 1000 1500 2000 2500 3000 Elapsed Time (sec)
Notes: Initial moisture content back-calculated from final dry weight. B-value reached asymptote at approximately 80%. k = 9.7E-04 cm/sec
Permeability Test Results FIGURE Formosa Mine Douglas County, Oregon Project NumberTested By Test Date Reviewed By Review Date 3 97290 MAL 10/9/2013
BCR-4 Permeability.xlsx Sample Number: BCR-6 Sample Location: N/A Test Specifications Depth (ft): N/A B-Value (%): 79.5% Lab I.D. Number: BCR-6 Consolidation stress (psi): 3.4 Sample Description: SAND with gravel Cell pressure (psi): 75.8 Test Type: Constant Head Head pressure (psi): 72.4 Tail pressure (psi): 72.0 Sample Characteristics Pressure Difference (psi) 0.41 Length of specimen (in): 6.04 Head (in) 11.3 Diameter of specimen (in): 2.72 Gradient (in/in) 1.9 Dry Density (pcf): 79.4 Specific gravity 2.53 Void Ratio: 0.99
Initial moisture content Final moisture content Wt. of wet soil & tin (g)N/A Wt. of wet soil & tin (g) 963.51 Wt. of dry soil & tin (g)N/A Wt. of dry soil & tin (g) 826.40 Wt. of water (g) N/A Wt. of water (g) 137.11 Wt. of tin (g) N/A Wt. of tin (g) 175.56 Wt. of dry soil (g) 796.12 Wt. of dry soil (g) 650.84 Moisture content (%)30.20 Moisture content (%) 21.07
Elaps. Elaps. Direct Burette Rds B-Value Calculation: Permeability Date Time time time Head Tail Initial Final (cm/sec) (min) (sec) (cc) (cc) Trial 22 10/11/13 4:08:15 PM 12.0 720 225.9 95.8 Cell Pressure 79.4 83.3 10/11/13 4:10:15 PM 14.0 840 227.0 94.6 1.9E-04 Pore Pressure 75.9 78.9 10/11/13 4:12:15 PM 16.0 960 227.5 94.0 1.3E-04 B-value 76.9% 10/11/13 4:14:15 PM 18.0 1080 228.5 92.9 1.5E-04 Trial 23 10/11/13 4:16:15 PM 20.0 1200 229.6 91.9 1.4E-04 Cell Pressure 83.5 87.5 10/11/13 4:18:15 PM 22.0 1320 231.7 90.6 1.8E-04 Pore Pressure 80 83.2 10/11/13 4:20:15 PM 24.0 1440 232.8 89.6 1.2E-04 B-value 80.0% 10/11/13 4:22:15 PM 26.0 1560 233.7 88.7 1.1E-04 Trial 24 10/11/13 4:24:15 PM 28.0 1680 234.4 88.0 9.5E-05 Cell Pressure 87.5 91.4 10/11/13 4:26:15 PM 30.0 1800 235.0 87.3 8.6E-05 Pore Pressure 84.1 87.2 10/11/13 4:28:15 PM 32.0 1920 235.7 86.6 9.3E-05 B-value 79.5%
1.0E‐03 (cm/sec)
1.0E‐04 Permeability
1.0E‐05 800 1000 1200 1400 1600 1800 2000 Elapsed Time (sec) Notes: Initial moisture content back-calculated from final dry weight. B-value reached asymptote at approximately 80% k = 9.6E-05 cm/sec
Permeability Test Results FIGURE Formosa Mine Douglas County , Oregon Project NumberTested By Test Date Reviewed By Review Date 4 97290 MAL 10/11/2013
BCR-6 Permeability.xlsx Sample Number: CH-PRETREAT Sample Location: N/A Test Specifications Depth (ft): N/A B-Value (%): 92.2% Lab I.D. Number: CH-PRETREAT Consolidation stress (psi): 4.0 Sample Description: SAND with silt and gravel Cell pressure (psi): 69.1 Test Type: Constant Head Head pressure (psi): 65.1 Tail pressure (psi): 64.7 Sample Characteristics Pressure Difference (psi) 0.45 Length of specimen (in): 5.30 Head (in) 12.5 Diameter of specimen (in): 1.62 Gradient (in/in) 2.4 Dry Density (pcf): 53.8 Specific gravity 2.37 Void Ratio: 1.75
Initial moisture content Final moisture content Wt. of wet soil & tin (g)N/A Wt. of wet soil & tin (g) 730.05 Wt. of dry soil & tin (g)N/A Wt. of dry soil & tin (g) 574.25 Wt. of water (g) N/A Wt. of water (g) 155.80 Wt. of tin (g) N/A Wt. of tin (g) 210.40 Wt. of dry soil (g) 366.01 Wt. of dry soil (g) 363.85 Moisture content (%)63.60 Moisture content (%) 42.82
Elaps. Elaps. Direct Burette Rds B-Value Calculation: Permeability Date Time time time Head Tail Initial Final (cm/sec) (min) (sec) (cc) (cc) Trial 12 10/7/13 11:25:00 AM 10.0 600 244.8 202.2 Cell Pressure 52.4 57.5 10/7/13 11:30:00 AM 15.0 900 244.8 198.0 1.6E-04 Pore Pressure 48.5 53.3 10/7/13 11:35:00 AM 20.0 1200 247.0 195.4 2.0E-04 B-value 94.1% 10/7/13 11:40:00 AM 25.0 1500 248.9 193.6 1.9E-04 Trial 13 10/7/13 11:45:00 AM 30.0 1800 251.0 190.8 2.2E-04 Cell Pressure 57.4 62.4 10/7/13 11:50:00 AM 35.0 2100 252.5 189.3 1.5E-04 Pore Pressure 53.6 58.2 10/7/13 11:55:00 AM 40.0 2400 253.7 188.1 1.3E-04 B-value 92.0% 10/7/13 12:00:00 PM 45.0 2700 254.5 187.3 9.7E-05 Trial 14 10/7/13 12:05:00 PM 50.0 3000 256.1 185.8 1.5E-04 Cell Pressure 62.5 67.6 10/7/13 12:10:00 PM 55.0 3300 257.0 184.9 8.4E-05 Pore Pressure 58.5 63.2 10/7/13 12:15:00 PM 60.0 3600 258.2 183.8 1.1E-04 B-value 92.2% 1.0E‐03 (cm/sec)
1.0E‐04 Permeability
1.0E‐05 0 500 1000 1500 2000 2500 3000 3500 4000
Elapsed Time (sec)
Notes: Initial moisture content back-calculated from final dry weight. B-value reached asymptote at ~92%. Sample collapsed in one section during consolidation; permeability calculation based on minimum diameter. k = 1.1E-04 cm/sec
Permeability Test Results FIGURE Formosa Mine Douglas County, Oregon Project NumberTested By Test Date Reviewed By Review Date 5 97290 MAL 10/7/2013
CH-PRETREAT Permeability.xlsx U.S. SIEVE OPENING IN INCHES U.S. SIEVE NUMBERS HYDROMETER 4 2 1 1/2 3 6 10 16 30 50 100 200 6 3 1.5 3/4 3/8 4 8 14 20 40 60 140 100 95
90
85
80
75
70
65
60
55
50
45
PERCENT FINER BY WEIGHT PERCENT FINER 40
35
30
25
20
15
10
5 0 100 10 1 0.1 0.01 0.001 GRAIN SIZE IN MILLIMETERS GRAVEL SAND COBBLES SILT OR CLAY coarse fine coarse medium fine
Specimen Identification Classification % Moisture Spec. Gravity Dry Density (pcf) BCR-2 (10/24/2013) POORLY GRADED SAND with GRAVEL(SP) 16.06 2.69 102.9 BCR-4 (10/24/2013) POORLY GRADED GRAVEL with SAND(GP) 14.81 2.67 92.7 BCR-6 (10/24/2013) POORLY GRADED GRAVEL with SAND(GP) 11.19 2.64 107.4 CHIT-PRE POORLY GRADED GRAVEL with SAND(GP) 14.83 2.68 86.3 (10/24/2013)
Specimen Identification D60 D30 D10 %Gravel %Sand %Fines % Porosity Void Ratio BCR-2 (10/24/2013) 5.36 0.62 0.23 47.7 48.8 3.6 0.63 BCR-4 (10/24/2013) 5.73 0.72 0.25 52.6 43.8 3.6 0.81 BCR-6 (10/24/2013) 5.64 0.65 0.26 51.2 46.6 2.2 0.53 CHIT-PRE 6.05 1.28 0.29 58.2 39.8 2.0 0.94 (10/24/2013) GRAIN SIZE DISTRIBUTION EPA Region 10 Formosa Mine Douglas County, Oregon
Project No: 97290 Figure: 1 GSA_SPG_N_DRYDEN_MC_LONG_ID FORMOSA LAB DATA.GPJREV. GINT STD US LAB.GDT2/25/14 Sample Number: BCR-2 Sample Date: 10/24/2013 Test Specifications Depth (ft): N/A B-Value (%): 78.3% Lab I.D. Number: BCR-2 (2) Consolidation stress (psi): 5.1 Sample Description: SAND with gravel Cell pressure (psi): 68.1 Test Type: Constant Head Head pressure (psi): 63.0 Tail pressure (psi): 62.6 Sample Characteristics Pressure Difference (psi) 0.40 Length of specimen (in): 3.74 Head (in) 11.0 Diameter of specimen (in): 1.88 Gradient (in/in) 2.9 Dry Density (pcf): 102.9 Specific gravity 2.69 Void Ratio: 0.63
Initial moisture content Final moisture content Wt. of wet soil & tin (g)N/A Wt. of wet soil & tin (g) 537.23 Wt. of dry soil & tin (g)N/A Wt. of dry soil & tin (g) 491.10 Wt. of water (g) N/A Wt. of water (g) 46.13 Wt. of tin (g) N/A Wt. of tin (g) 212.33 Wt. of dry soil (g) 281.52 Wt. of dry soil (g) 278.77 Moisture content (%)16.06 Moisture content (%) 16.55
Elaps. Elaps. Direct Burette Rds B-Value Calculation: Permeability time time Head Tail Initial Final (cm/sec) Date Time (min) (sec) (cc) (cc) Trial 17 1/8/14 9:08:10 AM 0.0 0 270.0 289.1 Cell Pressure 63.8 67.7 1/8/14 9:23:10 AM 15.0 900 294.3 265.1 4.7E-04 Pore Pressure 60.3 63.2 1/8/14 9:28:10 AM 20.0 1200 300.6 259.1 3.3E-04 B-value 74.5% 1/8/14 9:33:10 AM 25.0 1500 305.9 255.5 2.8E-04 Trial 18 1/8/14 9:38:10 AM 30.0 1800 309.6 250.1 2.9E-04 Cell Pressure 67.7 71.7 1/8/14 9:43:10 AM 35.0 2100 314.1 245.9 2.7E-04 Pore Pressure 64.2 67.3 1/8/14 9:48:10 AM 40.0 2400 317.0 241.5 2.3E-04 B-value 76.6% 1/8/14 9:50:10 AM 42.0 2520 318.4 240.1 2.3E-04 Trial 19 1/8/14 9:52:10 AM 44.0 2640 319.9 238.7 2.3E-04 Cell Pressure 71.7 76.2 1/8/14 9:55:10 AM 47.0 2820 322.0 236.5 2.3E-04 Pore Pressure 68.2 71.8 1/8/14 9:58:10 AM 50.0 3000 323.7 234.8 2.3E-04 B-value 78.3%
1.0E‐03 (cm/sec)
Permeability
1.0E‐04 0 500 1000 1500 2000 2500 3000 Elapsed Time (sec)
Notes: Initial moisture content back-calculated from final dry weight. B-value approached asymptote of approximately 80%. k = 2.3E-04 cm/sec
Permeability Test Results FIGURE Formosa Mine Douglas County, Oregon Project NumberTested By Test Date Reviewed By Review Date 2 97290MAL 1/8/2014 KIS 1/29/2014
POST-BCR-2 Permeability.xlsx Sample Number: BCR-4 Sample Date: 10/24/2013 Test Specifications Depth (ft): N/A B-Value (%): 75.8% Lab I.D. Number: BCR-4 (2) Consolidation stress (psi): 4.3 Sample Description: GRAVEL with sand Cell pressure (psi): 69.6 Test Type: Constant Head Head pressure (psi): 65.3 Tail pressure (psi): 64.8 Sample Characteristics Pressure Difference (psi) 0.53 Length of specimen (in): 4.20 Head (in) 14.6 Diameter of specimen (in): 1.87 Gradient (in/in) 3.5 Dry Density (pcf): 92.7 Specific gravity 2.67 Void Ratio: 0.80
Initial moisture content Final moisture content Wt. of wet soil & tin (g)N/A Wt. of wet soil & tin (g) 528.62 Wt. of dry soil & tin (g)N/A Wt. of dry soil & tin (g) 481.28 Wt. of water (g) N/A Wt. of water (g) 47.34 Wt. of tin (g) N/A Wt. of tin (g) 205.19 Wt. of dry soil (g) 279.44 Wt. of dry soil (g) 276.09 Moisture content (%)14.81 Moisture content (%) 17.15
Elaps. Elaps. Direct Burette Rds B-Value Calculation: Permeability Date Time time time Head Tail Initial Final (cm/sec) (min) (sec) (cc) (cc) Trial 20 1/7/14 9:08:10 AM 0.0 0 142.4 245.1 Cell Pressure 70.4 73.5 1/7/14 9:10:10 AM 2.0 120 147.3 239.6 1.0E-03 Pore Pressure 67.05 69.4 1/7/14 9:12:10 AM 4.0 240 150.8 236.7 8.6E-04 B-value 77.0% 1/7/14 9:14:10 AM 6.0 360 154.2 232.2 8.1E-04 Trial 21 1/7/14 9:18:10 AM 10.0 600 172.7 214.6 1.1E-03 Cell Pressure 63.4 67.1 1/7/14 9:23:10 AM 15.0 900 190.7 195.4 9.9E-04 Pore Pressure 59.94 62.78 1/7/14 9:28:10 AM 20.0 1200 206.9 176.6 9.3E-04 B-value 75.7% 1/7/14 9:33:10 AM 25.0 1500 221.3 163.1 7.6E-04 Trial 22 1/7/14 9:38:10 AM 30.0 1800 234.0 150.0 7.3E-04 Cell Pressure 67.1 70.7 1/7/14 9:43:10 AM 35.0 2100 246.5 138.0 7.0E-04 Pore Pressure 63.67 66.42 1/7/14 9:48:10 AM 40.0 2400 253.7 130.8 5.7E-04 B-value 75.8%
1.0E‐02 (cm/sec)
1.0E‐03 Permeability
1.0E‐04 0 500 1000 1500 2000 2500 Elapsed Time (sec)
Notes: Initial moisture content back-calculated from final dry weight. B-value reached asymptote at approximately 78%. k = 6.9E-04 cm/sec
Permeability Test Results FIGURE Formosa Mine Douglas County, Oregon Project NumberTested By Test Date Reviewed By Review Date 3 97290MAL 1/7/2014 KIS 1/29/2014
POST-BCR-4 Permeability.xlsx Sample Number: BCR-6 Sample Date: 10/24/2013 Test Specifications Depth (ft): N/A B-Value (%): 91.4% Lab I.D. Number: BCR-6 (2) Consolidation stress (psi): 4.0 Sample Description: GRAVEL with sand Cell pressure (psi): 76.6 Test Type: Constant Head Head pressure (psi): 72.5 Tail pressure (psi): 72.1 Sample Characteristics Pressure Difference (psi) 0.39 Length of specimen (in): 4.22 Head (in) 10.8 Diameter of specimen (in): 1.86 Gradient (in/in) 2.6 Dry Density (pcf): 107.4 Specific gravity 2.64 Void Ratio: 0.53
Initial moisture content Final moisture content Wt. of wet soil & tin (g)N/A Wt. of wet soil & tin (g) 561.58 Wt. of dry soil & tin (g)N/A Wt. of dry soil & tin (g) 514.22 Wt. of water (g) N/A Wt. of water (g) 47.36 Wt. of tin (g) N/A Wt. of tin (g) 213.82 Wt. of dry soil (g) 324.35 Wt. of dry soil (g) 300.40 Moisture content (%)11.19 Moisture content (%) 15.77
Elaps. Elaps. Direct Burette Rds B-Value Calculation: Permeability Date Time time time Head Tail Initial Final (cm/sec) (min) (sec) (cc) (cc) Trial 19 1/14/14 9:08:10 AM 0.0 0 288.0 156.0 Cell Pressure 65.9 69.5 1/14/14 9:13:10 AM 5.0 300 305.9 135.5 1.5E-03 Pore Pressure 62.6 65.69 1/14/14 9:18:10 AM 10.0 600 318.5 122.4 1.4E-03 B-value 86.3% 1/14/14 9:23:10 AM 15.0 900 336.6 105.6 1.7E-03 Trial 20 1/14/14 9:28:10 AM 20.0 1200 352.7 88.7 1.2E-03 Cell Pressure 69.8 73.1 1/14/14 9:33:10 AM 25.0 1500 366.3 74.9 1.1E-03 Pore Pressure 66.05 68.94 1/14/14 9:38:10 AM 30.0 1800 381.6 58.8 1.1E-03 B-value 87.6% 1/14/14 9:43:10 AM 35.0 2100 396.0 45.6 1.0E-03 Trial 21 1/14/14 9:48:10 AM 40.0 2400 407.7 32.4 8.9E-04 Cell Pressure 73.2 76.5 1/14/14 9:53:10 AM 45.0 2700 418.5 21.6 8.0E-04 Pore Pressure 69.41 72.5 1/14/14 9:58:10 AM 50.0 3000 429.3 10.8 8.0E-04 B-value 91.4%
1.0E‐02 (cm/sec)
1.0E‐03 Permeability
1.0E‐04 0 500 1000 1500 2000 2500 3000 Elapsed Time (sec)
Notes: Initial moisture content back-calculated from final dry weight. k = 8.8E-04 cm/sec
Permeability Test Results FIGURE Formosa Mine Douglas County, Oregon Project NumberTested By Test Date Reviewed By Review Date 4 97290MAL 1/14/2014 KIS 1/29/2014
POST-BCR-6 Permeability.xlsx Sample Number: CHIT-PRE Sample Date: 10/24/2013 Test Specifications Depth (ft): N/A B-Value (%): 59.0% Lab I.D. Number: CHIT-PRE Consolidation stress (psi): 3.2 Sample Description: GRAVEL with sand Cell pressure (psi): 63.7 Test Type: Constant Head Head pressure (psi): 60.5 Tail pressure (psi): 60.1 Sample Characteristics Pressure Difference (psi) 0.44 Length of specimen (in): 4.87 Head (in) 12.2 Diameter of specimen (in): 1.88 Gradient (in/in) 2.5 Dry Density (pcf): 86.3 Specific gravity 2.68 Void Ratio: 0.94
Initial moisture content Final moisture content Wt. of wet soil & tin (g)N/A Wt. of wet soil & tin (g) 576.33 Wt. of dry soil & tin (g)N/A Wt. of dry soil & tin (g) 510.77 Wt. of water (g) N/A Wt. of water (g) 65.56 Wt. of tin (g) N/A Wt. of tin (g) 209.73 Wt. of dry soil (g) 305.39 Wt. of dry soil (g) 301.04 Moisture content (%)14.83 Moisture content (%) 21.78
Elaps. Elaps. Direct Burette Rds B-Value Calculation: Permeability Date Time time time Head Tail Initial Final (cm/sec) (min) (sec) (cc) (cc) Trial 13 1/2/14 1:48:00 PM 0.0 0 270.8 173.6 Cell Pressure 52.2 56.0 1/3/14 1:49:00 PM 1.0 60 275.0 168.9 1.7E-03 Pore Pressure 49 51.2 1/4/14 1:50:00 PM 2.0 120 278.8 165.8 1.7E-03 B-value 57.9% 1/5/14 1:52:00 PM 4.0 240 286.4 158.7 1.8E-03 Trial 14 1/6/14 1:54:00 PM 6.0 360 293.2 149.8 2.1E-03 Cell Pressure 56.0 59.9 1/7/14 1:58:00 PM 10.0 600 307.8 135.5 1.7E-03 Pore Pressure 52.8 55.1 1/8/14 2:03:00 PM 15.0 900 331.2 110.3 1.8E-03 B-value 59.0% 1/9/14 2:08:00 PM 20.0 1200 361.8 83.9 1.8E-03 Trial 15 1/10/14 2:13:00 PM 25.0 1500 388.8 56.3 2.0E-03 Cell Pressure 56.0 59.9 1/11/14 2:18:00 PM 30.0 1800 412.2 32.4 1.8E-03 Pore Pressure 56.8 59.1 1/12/14 2:23:00 PM 35.0 2100 441.0 6.0 2.1E-03 B-value 59.0% 1.0E‐02 (cm/sec)
1.0E‐03 Permeability
1.0E‐04 0 500 1000 1500 2000 2500
Elapsed Time (sec)
Notes: Initial moisture content back-calculated from final dry weight. B-value would not increase above 59.0%. k = 1.9E-03 cm/sec
Permeability Test Results FIGURE Formosa Mine Douglas County, Oregon Project NumberTested By Test Date Reviewed By Review Date 5 97290MAL 1/2/2014 KIS 1/29/2014
CHIT-PRE Permeability.xlsx
Appendix B Formosa Mine Treatability Study Data Evaluation
Memorandum
To: Michael Allen, P.E., CDM Smith
From: Kimberly Zilis
Date: February 3, 2014
Subject: Formosa Mine Treatability Study Data Evaluation
Introduction The Office of Research and Development (ORD), in Cincinnati, Ohio, provided analytical support for the Formosa Treatability Study under the ORD Quality Assurance Project Plan (QAPP), Revision 1, April 26, 2012. In accordance with the Formosa Final Treatability Study QAPP, July 5, 2013, a Level 2A validation has been performed for all data. Laboratory results have been reviewed for compliance with project objectives. Data have been qualified in accordance with the United States Environmental Protection Agency Contract Laboratory Program National Functional Guidelines for Inorganic Superfund Data Review, Final (EPA 2010) (National Functional Guidelines), with method‐specific requirements superseding the National Functional Guidelines (NFGs). The qualified data are presented for each sampling event in Table A1.
Field and Laboratory Quality Assurance Activities Samples were collected from Biochemical Reactors (BCRs) 1 through 6, the successive alkalinity producing system (SAPS) pretreatment, the ChitoRem® pretreatment, and the influent water, which consisted of Formosa Adit water collected over a period of time into the influent barrel. These samples were collected for five rounds of sampling, after which the treatability study was disassembled. This study data evaluation memorandum is an appendix to the treatability study report, which describes the study details and any deviations from the treatability study QAPP.
ORD performed metals analyses on the total and dissolved fractions of each of the samples. Analyses were performed by the following methods:
. EPA SW‐846 6010 for metals . EPA SW‐846 7470 for mercury . EPA 300.0 for anions: chloride, fluoride, and sulfate . HACH Method 8131 for sulfide . Standard Methods SM 5560 D for volatile fatty acids . EPA method 150.1 for pH . EPA method 310.1 for alkalinity
Formosa Treatability Study Data Evaluation February 5, 2014 Page 2
Mercury analysis was performed for samples in round 1 and 2. Mercury was not detected in any sample in either of the first two rounds, and mercury analysis was dropped for subsequent rounds.
In Round 4 of the study, analysis for low level mercury and methylmercury were performed. The influent analysis from the Formosa 1 Adit was performed by Battelle. The effluent samples from each BCR were analyzed by the EPA Manchester Environmental Laboratory (MEL). Analyses were performed by the following methods:
. EPA SW‐846 1630 for low level mercury . EPA SW‐846 1631 for methylmercury
Field Quality Control As described in the Formosa Treatability Study QAPP, field duplicates were collected from BCR1 for each sampling round. Extra sample volume was collected from the adit water influent barrel for matrix spike (MS) and matrix spike duplicate (MSD) analyses. However, the extra volume was analyzed as a separate sample in the first three sampling events, effectively resulting in a second field duplicate. For Rounds 4 and 5, metals matrix spike analyses were performed on the extra sample volume provided. Matrix spikes were not performed for the other methods.
Laboratory Quality Control Laboratory quality control was performed in accordance with the ORD QAPP. Method blank and laboratory control sample (LCS) results were provided in the electronic data deliverable (EDD) report. Matrix spike results for metals were included in sampling events 4 and 5, for the total metals only in event 4, and total and dissolved metals analyses in event 5.
Data Quality Indicators Data quality and usability were determined based on various quality measures, commonly referred to as Data Quality Indicators (DQIs): precision, accuracy, representativeness, comparability, completeness, and sensitivity. These indicators are referred to as the PARCCS parameters. The PARCCS parameters are defined in the following sections. The quality control (QC) parameters evaluated in the data review, and their relation to the each parameter, are summarized in Table A2.
Results provided by the ORD include sample data, method blank results, LCS results, and MS results for metals analyses. Results were discussed in the case narratives when there were outliers.
Precision Influent adit water was collected in duplicate for each round of sampling, and extra sample volume was collected for MS analysis from BCR 1. MS analyses were not performed, or not reported, for rounds 1 through 3, and the extra sample volume provided was analyzed as an extra
Formosa Treatability Study Data Evaluation February 5, 2014 Page 3 sample, effectively resulting in two field duplicates for each sampling round. For round 4 and round 5, an MS was performed with the extra sample volume from BCR 1.
All field duplicate data compared well. MSDs were reported for the dissolved metals in sampling event 5 only, and therefore, precision data were generally measured by field duplicates.
Accuracy The aluminum MS percent recovery (%R) was 58 percent in round 4. Aluminum data in this round were qualified as estimated (J‐/UJ).
LCS results were provided for the metals analyses. All LCS results were within acceptance limits with the following exceptions:
Round 1 ‐ The %R for barium exceeded the acceptance limit in the LCS. All positive results for barium were qualified as estimated (J+). Silver was not spiked in the LCS. Silver results were not qualified on this basis.
Round 2 ‐ The %R of sodium, at 66 percent, was less than the lower acceptance limit of 70 percent in the LCS. ORD stated in the narrative that this recovery is not applicable due to the low spiking concentration (2.0 milligrams per liter [mg/L]), relative to the MRL (1.52 mg/L). CDM Smith agreed that the spiked concentration was low in comparison to the MRL, and the data were not qualified. By round 3, the LCS spike concentration was increased from 2 mg/L to 5 mg/L.
Round 4 ‐ The %R of sodium, at 152 percent, exceeded the acceptance limit of 130 percent in the LCS. The matrix spike levels for sodium were less than 4 times the native concentration, and data were not qualified.
The results for bottle blanks provided from the field and laboratory method blanks were reported. Target compounds greater than the ORD MRL were reported in the blanks.
The NFGs indicate that sample concentrations within 10 times the concentration reported in the blank be qualified as undetected at the level reported in the sample. In the interest of maximizing the usable data for the treatability study, this approach was modified. Sample results less than or equal to the concentration reported in the blank were qualified as undetected at the concentration reported. When blank results were greater than the MRL, associated sample data within 10 times the blank results were qualified as estimated with a possible high bias (J+), thus, flagging the results as having a potentially high bias due to high blank results, without actually discarding the data. Blank concentrations and associated qualifiers, if applicable, are presented below:
Formosa Treatability Study Data Evaluation February 5, 2014 Page 4
Round 1 – Calcium, potassium, and magnesium were detected in the method blank at 1.27 mg/L, 1.1 mg/L, and 0.33 mg/L, with MRLs of 0.285 mg/L, 0.945 mg/L, and 0.011 mg/L, respectively. The total potassium result in Adit 01‐09, was qualified as estimated with a possible high bias (J+). All other sample data results were well above those concentrations, and no qualifiers were applied.
Round 2 – Aluminum was reported in the total fraction method blank at 0.268 mg/L and the dissolved field blank at 0.293 mg/L, with an MRL of 0.105 mg/L. All aluminum data within 10 times these values were qualified as estimated with a possible high bias (J+).
Round 3 – Aluminum was reported in the field blank at 0.135 and 0.161 mg/L for the total and dissolved fractions, respectively. The case narrative notes that aluminum was also greater than the MRL in the continuing calibration blanks (CCB). All aluminum data within 10 times these values were qualified as estimated with a possible high bias (J+). Zinc was reported in the method blank at 0.009 mg/L and in the field blank at 0.016 mg/L, with an MRL of 0.006 mg/L. All zinc data within 10 times these values were qualified as estimated with a possible high bias (J+).
Round 4 – Aluminum was reported in the dissolved fraction of the field blank at 0.218 mg/L. All dissolved aluminum data less than 2.18 mg/L were qualified as estimated with a possible high bias (J+). Total silver was reported in the method blank at 0.009 mg/L and in the field blank at 0.01 mg/L, with an MRL of 0.003 mg/L. All data were less than 0.010 mg/L, and all positive results were qualified as undetected (U) at the level reported. The case narrative notes that cadmium and cobalt exceeded the MRL in the CCBs. Cadmium and cobalt data were estimated with a possible high bias (J+). The narrative also notes that nickel exceeded the MRL in the CCBs. Nickel data were estimated with a high possible bias (J+). Zinc was reported in the field blank at 0.006 and 0.284 mg/L for the total and dissolved fractions, respectively, with an MRL of 0.006 mg/L. Dissolved zinc data less than the 0.284 mg/L reported in the field blank were qualified as undetected (U). Zinc data within 10 times these values were qualified as estimated with a possible high bias (J+).
Round 5 – Iron, sodium, and zinc were detected in the method blank at 0.119 mg/L, 3.82 mg/L, and 0.015 mg/L, with MRLs of 0.117 mg/L, 1.52 mg/L, and 0.006 mg/L, respectively. All results less than 10 times these values were qualified as estimated with a possible high bias (J+). Most total zinc data were above 0.015 mg/L; however, the zinc data that were within 10 times that concentration (0.15) were estimated with a possible high bias (J+). Barium, iron, magnesium, sodium, and zinc were reported in the dissolved fraction field blank at 0.517, 0.111, 0.017, 1.71, and 0.305 mg/L, respectively. Concentrations in the sample less than these concentrations were qualified as undetected (U). Concentrations in the dissolved samples within 10 times these concentrations were qualified as estimated with a possible high bias (J+).
Formosa Treatability Study Data Evaluation February 5, 2014 Page 5
Representativeness Samples were collected and delivered to the laboratory under appropriate chain of custody criteria. All samples were analyzed by appropriate methods and within holding times. All preservation criteria were met. Therefore, the data should represent, as near as possible, the actual field conditions at the time of sampling.
Representativeness has been achieved by the performed field work and laboratory analyses. The analytical data generated are viewed to be a representative characterization of the treatability study sample chemistry.
Comparability Because of the abbreviated level of analytical documentation from the ORD laboratory in regards to raw data, calibration, and quality control samples, as well as the observed difficult matrix of the samples, samples for round 5 were split and submitted to a Contract Laboratory Program (CLP) laboratory as well as ORD. Chemtech Consulting Group, Mountainsides, NJ, performed the CLP analyses and EPA laboratory Manchester Environmental Laboratory performed alkalinity and anion analyses. Sulfides and volatile fatty acid analyses were not duplicated. Table A3 presents the split sample results. There are no criteria specified for the comparison of field splits sent to different laboratories. Most results compared within a factor of two. Otherwise, when the RPD was greater than 100 percent, the RPD is presented in bold.
Sensitivity According to the ORD QAPP, the MRL is set to three times the method detection limit (MDL). A number of the ORD MRLs are higher than the reporting limit criteria outlined in the treatability study work plan. Also, some of the ORD MRLs are higher than the Inductively Coupled Plasma‐ Atomic Emission Spectrometry (ICP‐AES) CLP Contract Required Quantitation Limits (CRQLs). For comparison, CLP CRQLs are listed in the undetected CLP values in Table A3, and the ORD MRLs are presented in the dissolved reporting limits in Table A1. For the work plan defined target metals, criteria for dissolved lead is 0.0043 mg/L. The ORD MRL is 0.017 mg/L. The CLP ICP‐AES CRQL is 0.01 mg/L, and the CLP ICP‐MS CRQL is 0.001 mg/L. All ORD data are from ICP‐ AES instrumentation. Through the CLP program, ICP‐Mass Spectrometry (ICP‐MS) analysis would be required to attain the work plan target reporting limit.
Data Usability Data have been qualified as summarized above and shown in Table A1. All data for the treatability study are considered usable. The CLP data in round 5 were validated by EPA Region 10 and are considered usable.
Table A1 Round 1 - July 15, 2013
Dissolved Reporting Location Limit Field Blank Method Blank Adit 01-09 ChitRem Pre 01-07 SAPS Pre 01-08 BCR1 01-01 BCR2 01-02 BCR3 01-03 BCR4 01-04 BCR5 01-05 BCR6 01-06 Total/Dissolved TDTDTD TDTDTDTDT DTDTDTD Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.095 0.105 U 0.095 U 0.105 U -- 14.1 14.2 1.02 0.755 0.954 0.095 1.05 0.095 4.49 4.2 1.61 0.34 3.52 3.06 2.11 1.23 4.8 4.8 Antimony mg/L 0.095 0.106 U 0.095 U 0.106 U -- 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.036 0.04 U 0.036 U 0.04 U -- 0.052 0.036 U 0.055 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 1.48 1.49 0.04 U 0.036 U 0.895 0.903 U 0.09 0.054 1.58 1.5 Barium mg/L 0.015 0.017 U 0.015 U 0.017 U -- 0.016 J+ 0.0172 0.202 J+ 0.148 0.149 J+ 0.075 0.213 J+ 0.056 0.672 J+ 0.532 0.486 J+ 0.283 0.495 J+ 0.407 0.697 J+ 0.423 0.679 J+ 0.588 Cadmium mg/L 0.002 0.003 U 0.002 U 0.003 U -- 0.192 0.194 0.003 U 0.002 U 0.014 0.003 0.011 0.002 U 0.021 0.016 0.019 0.002 U 0.02 0.005 0.013 0.002 U 0.03 0.025 Calcium mg/L 0.257 0.285 U 0.257 U 1.27 -- 96.6 98 1,010 883 198 191 241 238 3,020 3,390 397 381 2,310 2,500 1,170 1,110 3,530 3,750 Chromium mg/L 0.022 0.024 U 0.022 U 0.024 U -- 0.233 0.236 0.024 U 0.022 U 0.113 0.0981 0.039 0.022 U 0.035 0.0325 0.033 0.022 U 0.028 0.0227 0.032 0.022 U 0.045 0.0398 Cobalt mg/L 0.01 0.011 U 0.01 U 0.011 U -- 0.015 0.014 0.019 0.013 0.011 U 0.011 0.011 U 0.01 U 0.164 0.148 0.017 0.011 0.103 0.091 0.025 0.015 0.193 0.185 Copper mg/L 0.007 0.008 U 0.007 U 0.008 U -- 5.47 7.5 0.026 0.007 U 0.298 1.103 0.421 0.019 0.228 0.163 1.01 0.025 0.4 0.07 0.686 0.027 0.279 0.23 Iron mg/L 0.105 0.117 U 0.105 U 0.117 U -- 150 148 4.7 0.873 72 64.9 22 9.6 21.8 13.8 12.7 3.4 17.7 9.34 12.9 3.58 28.2 19.8 Lead mg/L 0.017 0.019 U 0.017 U 0.019 U -- 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.01 0.011 U 0.01 U 0.33 -- 21.9 21.8 155 127 52.4 49.7 114 118 917 849 251 241 745 690 490 462 1,100 1,040 Manganese mg/L 0.014 0.016 U 0.014 U 0.016 U -- 2.06 2.09 0.592 0.437 3.04 2.95 3.19 2.91 2.36 2.16 3.64 3.01 1.71 1.56 5.07 4.04 2.52 2.37 Mercury mg/L 0.139 0.139 U 0.139 U 0.139 U -- 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U Nickel mg/L 0.004 0.005 U 0.004 U 0.005 U -- 0.048 0.049 0.029 0.022 0.016 0.016 U 0.014 0.015 U 0.3223 0.313 0.044 0.035 0.21 0.202 0.061 0.052 0.402 0.398 Potassium mg/L 0.852 0.945 U 0.852 U 1.1 -- 1.84 J+ 2.32 88.9 76 76.4 74 496 532 730 693 1,040 1,010 780 738 1,240 1,200 991 937 Silver mg/L 0.003 0.003 U 0.003 U 0.003 U -- 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U Sodium mg/L 1.371 1.52 U 1.371 U 1.52 U -- 8.03 7.98 106 69.1 18 16.8 96.1 100 1,780 2,290 207 205 1,480 1,560 361 368 2,100 2,700 Vanadium mg/L 0.026 0.029 U 0.026 U 0.029 U -- 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.038 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.043 0.039 Zinc mg/L 0.005 0.009 0.009 0.006 U -- 62.1 72.5 0.159 0.058 12.1 8.64 3.88 0.121 1.05 0.56 6.64 0.193 2.63 0.32 5.92 0.195 0.924 0.606 General Chemistry Alkalinity, Total1 mg/L 5 60 -- NR -- 5 U -- 5,000 -- 400 -- 2,000 -- 30,000 -- 5,000 -- 20,000 -- 13,000 -- 32,000 -- pH SU NA 4.52 -- NR -- 3.18 -- 7.25 -- 6.09 -- 6.36 -- 6.51 -- 6.67 -- 6.82 -- 6.71 -- 6.87 -- Sulfide mg/L 0.01 NR -- NR -- NR -- NR -- NR -- NR -- NR -- -- NR -- NR -- NR -- Chloride mg/L 1.14 1.14 U -- 0.114 U -- 4.48 -- 18.76 -- 11.01 -- 75.12 -- 3,800 -- 242 -- 2,470 -- 332 -- 4,613 -- Fluoride mg/L 0.22 0.22 U -- 0.22 U -- 1.26 -- 0.22 U -- 0.49 -- 0.22 U -- 0.22 U -- 0.22 U -- 0.22 U -- 0.22 U -- 0.22 U -- Sulfate mg/L 3.31 3.31 U -- 0.331 U -- 1,765 -- 679 -- 801 -- 719 -- 1,367 -- 421 -- 948 -- 344 -- 1,284 -- Volatile Fatty Acids Acetic acid mg/L 3 3 U -- 0.98 U ------781 -- 13,400 -- 1,572 -- 7,760 -- 5,280 -- 16,680 -- Propionic acid mg/L 3.9 3.9 U -- 0.28 U ------233 -- 1,778 J -- 512 -- 2,140 J -- 1,069 J -- 2,663 J -- iso-Butyric acid mg/L 4.4 4.4 U -- 0.17 U ------44 U -- 1,054 J -- 62.7 -- 549.5 -- 343.3 -- 1,222 J -- Butyric acid mg/L 4.4 4.4 U -- 0.23 U ------136 -- 2,946 J -- 182.7 -- 1,464 J -- 850 -- 3,547 J -- iso-Valeric acid mg/L 5.3 5.3 U -- 0.19 U ------53 U -- 1,611 J -- 105 -- 786 -- 564 -- 1,834 J -- Valeric acid mg/L 5.3 5.3 U -- 0.19 U ------53 U -- 161 -- 41.4 -- 130 -- 147 -- 315 -- iso-Caproic acid mg/L 5.8 5.8 U -- 0.2 U ------58 U -- 473 -- 9.36 -- 251 -- 66.5 -- 500 -- Caproic acid mg/L 5.8 5.8 U -- 0.19 U ------58 U -- 58 U -- 58 U -- 58 U -- 58 U -- 58 U -- Heptanoic acid mg/L 6.6 6.6 U -- 1.76 ------66 U -- 66 U -- 66 U -- 66 U -- 66 U -- 66 U --
Notes: Q = Laboratory qualifier µg/L = micrograms per liter U = Below detection limit (reporting limit shown) mg/L = milligrams per liter J = Estimated value µS/cm = microSiemens per centimeter NR = Not reported su = standard units 1 Red font - validation qualifiers = units are mg/L as CaCO3 T = Total Fraction NA = Not Applicable D = Dissolved Fraction -- = Not analyzed
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table A1 Round 2 - July 23, 2013
Dissolved Reporting Location Limit Field Blank Method Blank Adit 02-09 ChitRem Pre 02-07 SAPS Pre 02-08 BCR1 02-01 BCR2 02-02 BCR3 02-03 BCR4 02-04 BCR5 02-05 BCR6 02-06 Total/Dissolved TDTDTDT D T DTDTDTDT DTDTD Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.095 0.105 U 0.293 0.268 -- 13.9 13.8 0.9 J+ 0.941 J+ 2.6 J 0.518 J+ 1.99 J 0.309 J+ 3.58 3.74 0.47 J+ 0.367 J+ 2.82 2.61 J 1.07 J+ 0.981 J+ 2.92 2.82 J+ Antimony mg/L 0.095 0.106 U 0.095 U 0.106 U -- 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.036 0.04 U 0.036 U 0.04 U -- 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.264 0.29 0.04 U 0.036 U 0.098 0.052 U 0.04 U 0.036 U 0.053 0.036 U Barium mg/L 0.015 0.017 U 0.015 U 0.017 U -- 0.018 0.015 U 0.138 0.143 0.058 0.055 0.13 0.126 0.497 0.477 0.176 0.094 0.406 0.381 0.276 0.258 0.474 0.465 Cadmium mg/L 0.002 0.003 U 0.002 U 0.003 U -- 0.181 0.186 0.003 U 0.002 U 0.047 0.044 0.01 0.004 0.003 U 0.004 0.003 U 0.002 U 0.003 U 0.002 U 0.013 0.002 U 0.003 U 0.002U Calcium mg/L 0.257 0.285 U 0.257 U 0.285 U -- 108 105 812 817 183 181 198 198 2,790 2,820 240 239 2,130 2,030 901 891 2,300 2,250 Chromium mg/L 0.022 0.024 U 0.022 U 0.024 U -- 0.264 0.261 0.024 U 0.022 U 0.228 0.215 0.212 0.21 0.024 U 0.014 0.072 0.069 0.024 U 0.022 U 0.024 U 0.022 U 0.024 U 0.022 U Cobalt mg/L 0.01 0.011 U 0.01 U 0.011 U -- 0.015 0.015 0.011 U 0.01 U 0.016 0.015 0.013 0.0125 0.04 0.043 0.011 U 0.01 U 0.018 0.012 0.011 U 0.01 U 0.011 U 0.01 U Copper mg/L 0.007 0.008 U 0.007 U 0.008 U -- 5.01 5.21 0.008 U 0.007 U 0.606 0.297 0.442 0.216 0.017 0.047 0.16 0.072 0.029 0.01 0.027 0.007 U 0.021 0.007 U Iron mg/L 0.105 0.117 U 0.105 U 0.117 U -- 158 152 2.89 0.143 140 133 127 126 6.34 6.27 45.2 43.6 4.99 2.68 0.658 0.105 U 2.87 0.622 Lead mg/L 0.017 0.019 U 0.017 U 0.019 U -- 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.01 0.011 U 0.01 U 0.011 U -- 23.1 22.5 39.4 38.7 25.4 25.5 26.2 26.3 371 352 33.8 32.9 216 191 65.5 57.4 149 146 Manganese mg/L 0.014 0.016 U 0.014 U 0.016 U -- 2.19 2.19 0.512 0.463 2.56 2.55 2.78 2.78 1.51 1.67 3.37 3.29 1.22 1.07 1.08 0.917 1.21 0.94 Mercury mg/L 0.139 0.139 U 0.139 U 0.139 U -- 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U 0.139 U Nickel mg/L 0.004 0.005 U 0.004 U 0.005 U -- 0.045 0.046 0.005 U 0.004 U 0.041 0.042 0.019 0.019 0.086 0.094 0.005 U 0.004 U 0.044 0.037 0.006 0.004 0.023 0.021 Potassium mg/L 0.852 0.945 U 0.852 U 0.945 U -- 1.89 1.81 4.33 5.01 5.82 6.28 9.31 8.72 218 232 25.3 19.9 179 169 51.9 42.3 37.4 36.1 Silver mg/L 0.003 NR NR NR -- NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Sodium mg/L 1.371 1.52 U 1.371 U 1.52 U -- 8.2 8.21 11.6 13.4 8.4 8.74 9.24 9.2 342 407 11.3 10.3 134 105 30.3 27.1 81.1 83.3 Vanadium mg/L 0.026 0.029 U 0.026 U 0.029 U -- 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U Zinc mg/L 0.005 0.006 U 0.012 0.006 U -- 64.5 63.8 0.031 0.009 53.9 54 17.6 15.16 0.085 0.367 5.82 0.116 0.282 0.034 0.185 0.007 0.111 0.025 General Chemistry Alkalinity, Total1 mg/L 5 60 -- NR -- 5 U -- 2,800 -- 125 -- 200 -- 17,800 -- 375 -- 14,000 -- 3,900 -- 11,700 -- pH SU NA 5.37 -- NR -- 3.3 -- 6.85 -- 5.33 -- 5.96 -- 6.74 -- 6.23 -- 6.82 -- 6.79 -- 6.58 -- Sulfide mg/L 0.01 0.01 U -- NR -- NR -- NR -- NR -- 0.33 -- 3.7 -- 2.9 -- 3.1 -- 39 -- 10 -- Chloride mg/L 1.14 1.14 U -- 0.114 U -- 2.8 -- 2.49 -- 2.8 -- 3.71 -- 493 -- 5.7 -- 238 -- 15.9 -- 65.4 -- Fluoride mg/L 0.22 0.22 U -- 0.22 U -- 1.8 -- 0.22 U -- 0.22 U -- 0.22 U -- 0.22 U -- 0.705 -- 0.22 U -- 0.22 U -- 0.22 U -- Sulfate mg/L 3.31 3.31 U -- 0.331 U -- 1,893 -- 541 -- 821 -- 987 -- 180 -- 547 -- 97.4 -- 288 -- 67.2 -- Volatile Fatty Acids Acetic acid mg/L 3 3 U -- 3 U ------29.6 9,967 85.7 6,378 1,150 8,162 Propionic acid mg/L 3.9 3.9 U -- 3.9 U ------3.9 U 1,950 U 4.15 1,950 U 58.3 699 iso-Butyric acid mg/L 4.4 4.4 U -- 4.4 U ------4.4 U 2,200 U 4.4 U 2,200 U 44 U 176 Butyric acid mg/L 4.4 4.4 U -- 4.4 U ------4.4 U 2,200 U 4.4 U 2,200 U 79.9 U 672 iso-Valeric acid mg/L 5.3 5.3 U -- 5.3 U ------5.3 U 2,650 U 5.3 U 2,650 U 66.5 282 Valeric acid mg/L 5.3 5.3 U -- 5.3 U ------5.3 U 2,650 U 5.3 U 2,650 U 53 U 175 iso-Caproic acid mg/L 5.8 5.8 U -- 5.8 U ------5.8 U 2,900 U 5.8 U 2,900 U 58 U 145 U Caproic acid mg/L 5.8 5.8 U -- 5.8 U ------5.8 U 2,900 U 5.8 U 2,900 U 58 U 145 U Heptanoic acid mg/L 6.6 6.6 U -- 6.6 U ------6.6 U 3,300 U 6.6 U 3,300 U 66 U 165 U
Notes: Q = Laboratory qualifier µg/L = micrograms per liter U = Below detection limit (reporting limit shown) mg/L = milligrams per liter J = Estimated value µS/cm = microSiemens per centimeter NR = Not reported su = standard units 1 Red font - validation qualifiers = units are mg/L as CaCO3 T = Total Fraction NA = Not Applicable D = Dissolved Fraction -- = Not analyzed
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table A1 Round 3 - August 6, 2013
Dissolved Reporting Location Limit Field Blank Method Blank Adit 03-09 ChitRem Pre 03-07 SAPS Pre 03-08 BCR1 03-01 BCR2 03-02 BCR3 03-03 BCR4 03-04 BCR5 03-05 BCR6 03-06 Total/Dissolved TDTDTDT D T DTDTDTDT DTDTD Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.095 0.135 0.161 0.105 U -- 13.6 13.4 0.449 J+ 0.511 J+ 3.91 0.5 J+ 3.19 0.988 J 2.03 J+ 1.9 J 0.242 J 0.245 J 1.48 1.54 J 0.473 J+ 0.46 J+ 2.71 2.48 J Antimony mg/L 0.095 0.106 U 0.095 U 0.106 U -- 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.036 0.04 U 0.036 U 0.04 U -- 0.055 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.264 0.036 U 0.04 U 0.036 U 0.098 0.037 0.04 U 0.036 U 0.053 0.071 Barium mg/L 0.015 0.017 U 0.015 U 0.017 U -- 0.017 0.017 0.158 0.133 0.071 0.069 0.108 0.104 0.29 0.257 0.175 0.172 0.311 0.295 0.18 0.174 0.636 0.613 Cadmium mg/L 0.002 0.003 U 0.002 U 0.003 U -- 0.16 0.163 0.003 U 0.002 U 0.021 0.022 0.019 0.016 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U Calcium mg/L 0.257 0.322 0.257 U 0.285 U -- 111 110 496 489 183 190 198 188 2,790 1,490 240 228 2,130 1,270 901 506 2,300 1,970 Chromium mg/L 0.022 0.024 U 0.022 U 0.024 U -- 0.254 0.25 0.0766 0.069 0.217 0.213 0.206 0.202 0.024 U 0.022 U 0.116 0.107 0.024 U 0.022 U 0.024 U 0.022 U 0.024 U 0.022 U Cobalt mg/L 0.01 0.011 U 0.01 U 0.011 U -- 0.018 0.017 0.011 U 0.01 U 0.019 0.017 0.015 0.0141 0.011 U 0.01 U 0.011 U 0.107 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U Copper mg/L 0.007 0.008 U 0.007 U 0.008 U -- 4.39 4.43 0.08 0.0704 0.606 0.23 0.442 0.214 0.017 0.007 U 0.16 0.113 0.029 0.007 U 0.027 0.007 U 0.021 0.007 U Iron mg/L 0.105 0.117 U 0.105 U 0.117 U -- 153 159 49.2 45.4 134 138 131 125 2.18 0.21 76.9 69.6 2.67 1.96 1.56 0.12 1.49 0.622 Lead mg/L 0.017 0.019 U 0.017 U 0.019 U -- 0.04 0.041 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.01 0.044 0.01 U 0.011 U -- 22.8 23.4 38.6 38.3 23.7 24.2 24.7 24.2 73.8 70 26.8 26.2 76.5 75 40.3 40.1 104 132 Manganese mg/L 0.014 0.016 U 0.014 U 0.016 U -- 2.19 2.17 2.42 2.37 2.58 2.57 2.5 2.51 0.807 0.5 3.22 3.16 1.62 1.61 1.67 1.615 1.06 0.926 Mercury mg/L 0.139 NR NR NR -- NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Nickel mg/L 0.004 0.005 U 0.004 U 0.005 U -- 0.041 0.042 0.005 U 0.004 U 0.036 0.038 0.021 0.021 0.011 0.01 0.005 U 0.004 U 0.013 0.013 0.005 U 0.004 U 0.019 0.024 Potassium mg/L 0.852 0.945 U 0.852 U 0.945 U -- 1.76 1.77 6.11 5.5 3.23 3.23 4.13 4.07 14 13 7.56 7.5 33 33 12.3 10.7 30.8 38 Silver mg/L 0.003 0.003 U 0.003 U 0.003 U -- 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U Sodium mg/L 1.371 1.52 U 1.371 U 1.52 U -- 8.94 9.1 19 16.9 9.17 9.25 9.26 9.24 26.6 26 9.29 9.5 40.3 41 19.3 18.9 62.6 103 Vanadium mg/L 0.026 0.029 U 0.026 U 0.029 U -- 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U Zinc mg/L 0.005 0.016 0.005 U 0.009 -- 68.4 66.5 0.022 J+ 0.006 49.8 48.7 29.9 27 0.229 0.059 1.77 0.256 0.016 J 0.005 U 0.041 J+ 0.006 0.067 J+ 0.005 U General Chemistry Alkalinity, Total1 mg/L 5 60 -- NR -- 5 U -- 1,400 -- 125 -- 125 -- 5,600 -- 300 -- 5,000 -- 1,700 -- 10,400 -- pH SU NA 5.26 -- NR -- 3.49 -- 6.25 -- 6.08 -- 5.91 -- 6.94 -- 6.22 -- 6.49 -- 6.47 -- 6.55 -- Sulfide mg/L 0.01 0.01 U -- NR -- NR -- NR -- NR -- 0.01 -- 1.7 -- 0.5 -- 6.3 -- 24 -- 10 -- Chloride mg/L 1.14 1.14 U -- 0.114 U -- 3.53 -- 6.72 -- 2.86 -- 3.25 -- 6.53 -- 2.88 -- 21.2 -- 10.5 -- 69.3 -- Fluoride mg/L 0.22 0.22 U -- 0.22 U -- 2.1 -- 0.22 U -- 1.66 -- 1.76 -- 0.22 U -- 1.06 -- 0.22 U -- 0.22 U -- 0.22 U -- Sulfate mg/L 3.31 3.31 U -- 0.331 U -- 1,840 -- 424 -- 809 -- 1,001 -- 495 -- 611 -- 133 -- 312 -- 44.7 -- Volatile Fatty Acids Acetic acid mg/L 3 3 U -- 3 U ------9.8 3,073 14.7 1,247 900 5,897 Propionic acid mg/L 3.9 3.9 U -- 3.9 U ------3.9 U 780 U 3.9 U 390 U 97.5 U 724 iso-Butyric acid mg/L 4.4 4.4 U -- 4.4 U ------4.4 U 880 U 4.4 U 440 U 110 U 440 U Butyric acid mg/L 4.4 4.4 U -- 4.4 U ------4.4 U 880 U 4.4 U 440 U 110 U 1,682 iso-Valeric acid mg/L 5.3 5.3 U -- 5.3 U ------5.3 U 1,060 U 5.3 U 530 U 132.5 U 530 U Valeric acid mg/L 5.3 5.3 U -- 5.3 U ------5.3 U 1,060 U 5.3 U 530 U 132.5 U 530 U iso-Caproic acid mg/L 5.8 5.8 U -- 5.8 U ------5.8 U 1,160 U 5.8 U 580 U 145 U 580 U Caproic acid mg/L 5.8 5.8 U -- 5.8 U ------5.8 U 1,160 U 5.8 U 580 U 145 U 580 U Heptanoic acid mg/L 6.6 6.6 U -- 6.6 U ------6.6 U 1,320 U 6.6 U 660 U 165 U 660 U
Notes: Q = Laboratory qualifier µg/L = micrograms per liter U = Below detection limit (reporting limit shown) mg/L = milligrams per liter J = Estimated value µS/cm = microSiemens per centimeter NR = Not reported su = standard units 1 Red font - validation qualifiers = units are mg/L as CaCO3 T = Total Fraction NA = Not Applicable D = Dissolved Fraction -- = Not analyzed
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table A1 Round 4 - August 20, 2013
Dissolved Reporting Location Limit Field Blank Method Blank Adit 04-09 ChitRem Pre 04-07 SAPS Pre 04-08 BCR1 04-01 BCR2 04-02 BCR3 04-03 BCR4 04-04 BCR5 04-05 BCR6 04-06 Total/Dissolved TDTD T DT D T DTDTDTDT DTDT D Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.095 0.105 U 0.218 0.105 U -- 13.6 J 13.6 0.42 J 0.285 3.78 J 0.695 J+ 1.51 J 0.486 J+ 1.79 J 1.52 J+ 0.105 UJ 0.183 J+ 1.11 J 0.81 J+ 0.483 J 0.219 J+ 1.34 J 1.07 J+ Antimony mg/L 0.095 0.106 U 0.095 U 0.106 U -- 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.036 0.04 U 0.036 U 0.04 U -- 0.054 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 0.036 U Barium mg/L 0.015 0.017 U 0.495 0.017 U -- 0.017 U 0.174 U 0.128 0.536 J+ 0.063 0.203 U 0.072 0.184 U 0.376 0.714 J+ 0.132 0.267 U 0.255 0.595 J+ 0.143 0.6 J+ 0.366 0.706 J+ Cadmium mg/L 0.002 0.003 U 0.002 U 0.003 U -- 0.154 0.155 0.003 U 0.002 U 0.012 J+ 0.012 J+ 0.006 J+ 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U Calcium mg/L 0.257 0.285 U 0.257 U 1.71 -- 117 112 411 393 203 191 194 188 1,654 1,530 244 235 1,122 913 467 445 1,310 1,220 Chromium mg/L 0.022 0.024 U 0.022 U 0.024 U -- 0.272 0.263 0.052 0.042 0.192 0.182 0.134 0.13 0.024 U 0.022 U 0.048 0.046 0.024 U 0.022 U 0.024 U 0.022 U 0.024 U 0.022 U Cobalt mg/L 0.01 0.011 U 0.01 U 0.011 U -- 0.012 J+ 0.012 J+ 0.011 U 0.01 U 0.014 J+ 0.011 J+ 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U Copper mg/L 0.007 0.008 U 0.007 U 0.008 U -- 4.24 4.14 0.051 0.041 0.287 0.185 0.249 0.134 0.01 0.007 U 0.046 0.043 0.011 0.007 U 0.013 0.007 U 0.008 U 0.007 U Iron mg/L 0.105 0.117 U 0.105 U 0.117 U -- 173 171 32.8 27.3 122 120 88.4 86.6 2.52 0.781 30 28.9 5.06 4.68 1.21 0.069 1.54 0.522 Lead mg/L 0.017 0.019 U 0.017 U 0.019 U -- 0.041 0.037 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.01 0.011 U 0.018 0.037 -- 25.8 25.9 37 37.3 27.1 27.2 25.7 26 101 104 26.4 26.5 67.6 56.3 41.9 40.9 91.5 91.8 Manganese mg/L 0.014 0.016 U 0.014 U 0.016 U -- 2.24 2.15 2.29 2.14 2.57 2.45 2.21 2.12 0.851 0.713 2.52 2.43 2.04 2.02 1.5 1.39 0.776 0.669 Mercury mg/L 0.139 NR NR NR -- NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Nickel mg/L 0.004 0.005 U 0.004 U 0.005 U -- 0.023 J+ 0.027 J+ 0.005 U 0.004 U 0.032 J+ 0.036 J+ 0.005 U 0.004 U 0.011 J+ 0.008 J+ 0.005 U 0.004 U 0.007 J+ 0.004 U 0.005 U 0.004 U 0.012 J+ 0.011 J+ Potassium mg/L 0.852 0.945 U 0.852 U 0.945 U -- 2.12 2.91 5.62 6.63 3.16 4.03 5.53 6.45 17.2 16.9 5.82 6.76 21 16.3 12.3 12.4 22.1 22.2 Silver mg/L 0.003 0.01 0.009 0.009 -- 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.004 U 0.004 U 0.009 U 0.006 U 0.006 U 0.003 U Sodium mg/L 1.371 1.62 1.371 U 1.52 U -- 12.2 11.5 20.2 19.8 10.3 11.7 10.1 11.6 49.6 48.1 10.1 11.5 20.2 18.1 22.4 23.1 50.6 48.4 Vanadium mg/L 0.026 0.029 U 0.026 U 0.029 U -- 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U Zinc mg/L 0.005 0.006 0.284 0.006 U -- 66.5 66 0.024 J+ 0.286 J+ 55.2 52.8 13.2 13.9 0.055 J+ 0.19 U 1.95 0.458 J+ 0.331 0.209 U 0.083 J+ 0.261 U 0.026 J+ 0.186 U General Chemistry Alkalinity, Total1 mg/L 5 60 -- NR -- 5 U -- 1,430 -- 60 -- 250 -- 6,300 -- 300 -- 5,900 -- 1,750 -- 7,300 -- pH SU NA 4.95 -- NR -- 3.51 -- 6.38 -- 6.08 -- 6.07 -- 6.7 -- 6.29 -- 6.42 -- 6.6 -- 6.54 -- Sulfide mg/L 0.01 0.01 U -- NR -- NR -- NR -- NR -- 0.01 U -- 1.5 -- 0.08 -- 1.9 -- 20 -- 4 -- Chloride mg/L 1.14 1.14 U -- 0.114 U -- 2.87 -- 4.34 -- 2.92 -- 2.9 -- 17.9 -- 2.72 -- 2.2 -- 7.5 -- 15.5 -- Fluoride mg/L 0.22 0.22 U -- 0.022 U -- 1.61 -- 0.22 U -- 1.81 -- 0.22 U -- 0.22 U -- 1.1 -- 0.22 U -- 0.22 U -- 0.22 U -- Sulfate mg/L 3.31 3.31 U -- 0.331 U -- 2,180 -- 114 -- 916 -- 670 -- 118 -- 440 -- 120 -- 32 -- 3.31 U -- Volatile Fatty Acids Acetic acid mg/L 3 3 U -- 3 U ------15.4 4,610 5.2 2,970 784 4,588 Propionic acid mg/L 3.9 3.9 U -- 3.9 U ------3.9 U 780 U 3.9 U 390 U 97.5 U 780 U iso-Butyric acid mg/L 4.4 4.4 U -- 4.4 U ------4.4 U 880 U 4.4 U 440 U 110 U 880 U Butyric acid mg/L 4.4 4.4 U -- 4.4 U ------4.4 U 880 U 4.4 U 440 U 110 U 880 U iso-Valeric acid mg/L 5.3 5.3 U -- 5.3 U ------5.3 U 1,060 U 5.3 U 530 U 132.5 U 1,060 U Valeric acid mg/L 5.3 5.3 U -- 5.3 U ------5.3 U 1,060 U 5.3 U 530 U 132.5 U 1,060 U iso-Caproic acid mg/L 5.8 5.8 U -- 5.8 U ------5.8 U 1,160 U 5.8 U 580 U 145 U 1,160 U Caproic acid mg/L 5.8 5.8 U -- 5.8 U ------5.8 U 1,160 U 5.8 U 580 U 145 U 1,160 U Heptanoic acid mg/L 6.6 6.6 U -- 6.6 U ------6.6 U 1,320 U 6.6 U 660 U 165 U 1,320 U Trace Mercury (Round 4) Total Mercury ng/L 0.53 0.53 U 0.53 U 2.18 1.02 J 14 J 0.65 J 22 J 8.9 J 12 J Methylmercury ng/L 0.05 0.05 U 0.05 U 0.05 U 1.19 0.0895 1.64 1.19 2.7
Notes: Q = Laboratory qualifier µg/L = micrograms per liter U = Below detection limit (reporting limit shown) mg/L = milligrams per liter J = Estimated value µS/cm = microSiemens per centimeter NR = Not reported su = standard units 1 Red font - validation qualifiers = units are mg/L as CaCO3 T = Total Fraction NA = Not Applicable D = Dissolved Fraction -- = Not analyzed
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table A1 Round 5 - September 4, 2013
Dissolved Reporting Location Limit Field Blank Method Blank Adit 05-09 ChitRem Pre 05-07 SAPS Pre 05-08 BCR1 05-01 BCR2 05-02 BCR3 05-03 BCR4 05-04 BCR5 05-05 BCR6 05-06 Total/Dissolved TDTD T DT D T DTDTDTDT DTD T D Chemical Units Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Results Q Metals/Metalloids Aluminum mg/L 0.095 0.105 U 0.095 U 0.105 U -- 12.6 12.4 0.105 U 0.095 U 2.42 12.4 1.72 1.55 0.105 U 0.095 U 0.105 U 0.095 U 0.105 U 0.095 U 0.105 U 0.095 U 0.105 U 0.095 U Antimony mg/L 0.095 0.106 U 0.095 U 0.106 U -- 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U 0.106 U 0.095 U Arsenic mg/L 0.036 0.04 U 0.036 U 0.04 U -- 0.051 0.039 0.04 U 0.036 U 0.04 U 0.039 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 U 0.036 U 0.04 0.045 Barium mg/L 0.015 0.017 U 0.517 0.017 U -- 0.017 U 0.108 U 0.097 0.652 J 0.056 0.243 U 0.144 0.13 U 0.206 0.562 J+ 0.157 0.132 U 0.21 0.382 U 0.146 0.659 J 0.359 0.755 J Cadmium mg/L 0.002 0.003 U 0.002 U 0.003 U -- 0.136 0.141 0.003 U 0.002 U 0.025 0.142 0.032 0.029 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U 0.003 U 0.002 U Calcium mg/L 0.257 0.285 U 0.257 U 0.285 U -- 106 102 212 208 186 102 201 181 703 766 242 238 764 603 303 286 943 924 Chromium mg/L 0.022 0.024 U 0.022 U 0.024 U -- 0.155 0.113 0.024 U 0.022 U 0.127 0.112 0.085 0.077 0.024 U 0.022 U 0.026 0.027 0.024 U 0.022 U 0.024 U 0.022 U 0.024 U 0.022U Cobalt mg/L 0.01 0.011 U 0.01 U 0.011 U -- 0.013 0.019 0.011 U 0.01 U 0.013 0.019 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U 0.011 U 0.01 U Copper mg/L 0.007 0.008 U 0.007 U 0.008 U -- 3.57 3.8 0.012 0.008 0.187 3.83 0.108 0.098 0.008 0.007 U 0.03 0.007 U 0.008 U 0.007 U 0.067 0.007 U 0.008 U 0.007 U Iron mg/L 0.105 0.122 0.111 0.119 -- 158 150 13.3 10.4 131 150 97.3 87.6 6.97 0.517 J+ 33.7 31.6 4.94 2.75 2.58 0.173 2.53 1.16 Lead mg/L 0.017 0.019 U 0.017 U 0.019 U -- 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U 0.019 U 0.017 U Magnesium mg/L 0.01 0.011 U 0.017 0.011 U -- 24.8 25.3 30.5 28.5 26.5 25.4 30 27 47.9 48.7 30.2 28 55.9 44.5 36 33 80.2 76.1 Manganese mg/L 0.014 0.016 U 0.014 U 0.016 U -- 2.09 2.11 1.44 1.37 2.39 2.1 2.67 2.404 0.668 0.648 2.81 2.74 1.56 1.64 1.34 1.2 0.735 0.679 Mercury mg/L 0.139 NR NR NR -- NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR NR Nickel mg/L 0.004 0.005 U 0.004 U 0.005 U -- 0.033 0.033 0.005 U 0.004 U 0.037 0.033 0.02 0.018 0.006 0.006 0.005 U 0.004 U 0.007 0.005 0.006 0.004 0.016 0.014 Potassium mg/L 0.852 0.945 U 0.852 U 0.945 U -- 2.03 2.47 3.13 3.6 2.5 2.53 3.51 3.16 6.67 7.15 3.57 3.91 10.6 7.64 8.1 7.83 17.4 17 Silver mg/L 0.003 0.003 U 0.003 U 0.003 U -- 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U 0.003 U Sodium mg/L 1.371 1.52 U 1.71 3.82 -- 9.81 J+ 13.1 J+ 12.7 J+ 14.7 J+ 9.8 J+ 13 J+ 13.8 J+ 12.4 J+ 23.2 J+ 26.4 9.94 J+ 11.8 J+ 15.1 J+ 15.7 J+ 19.2 J+ 20.6 37.6 J+ 37.2 Vanadium mg/L 0.026 0.029 U 0.026 U 0.029 U -- 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U 0.029 U 0.026 U Zinc mg/L 0.005 0.007 0.305 0.015 -- 64.1 61.5 0.026 J 0.311 J 57.3 65.1 28.7 26.1 0.035 J 0.241 U 2.58 0.667 J 0.09 J 0.26 U 0.519 0.307 U 0.034 J 0.22 U General Chemistry Alkalinity, Total1 mg/L 5 63 -- NR -- 5 U -- 1,310 -- 63 -- 125 -- 3,440 -- 250 -- 2,880 -- 1,630 -- 6,000 -- pH SU NA 5.55 -- NR -- 3.36 -- 6.44 -- 5.08 -- 5.67 -- 6.54 -- 6.3 -- 6.47 -- 6.68 -- 6.52 -- Sulfide mg/L 0.01 0.01 U -- NR -- NR -- NR -- NR -- 0.01 U -- 1 -- 0.16 -- 200 -- 125 -- 11 -- Chloride mg/L 1.14 0.11 U -- 0.114 U -- 3.75 -- 3.91 -- 3.59 -- 4.04 -- 5.1 -- 3.14 -- 1.54 -- 7.29 -- 7.03 -- Fluoride mg/L 0.22 0.031 -- 0.022 U -- 2.07 -- 1.08 -- 2.07 -- 1.58 -- 0.22 U -- 1.2 -- 0.22 U -- 0.64 -- 0.22 U -- Sulfate mg/L 3.31 0.33 U -- 0.331 U -- 2,004 -- 38.5 -- 1,003 -- 1,400 -- 3.31 U -- 610 -- 222 -- 30.3 -- 3.31 U -- Volatile Fatty Acids Acetic acid mg/L 3 3 U -- 3 U ------3 U 2,044 3 U 1,740 27.1 3,717 Propionic acid mg/L 3.9 3.9 U -- 3.9 U ------3.9 U 177 3.9 U 141 63.1 352 iso-Butyric acid mg/L 4.4 4.4 U -- 4.4 U ------4.4 U 44 U 4.4 U 48.9 29 213 Butyric acid mg/L 4.4 4.4 U -- 4.4 U ------4.4 U 188 4.4 U 139 36.8 827 iso-Valeric acid mg/L 5.3 5.3 U -- 5.3 U ------5.3 U 53 U 5.3 U 88.3 45.2 418 Valeric acid mg/L 5.3 5.3 U -- 5.3 U ------5.3 U 53 U 5.3 U 53 U 11.9 193 iso-Caproic acid mg/L 5.8 5.8 U -- 5.8 U ------5.8 U 58 U 5.8 U 58 U 5.8 U 58 U Caproic acid mg/L 5.8 5.8 U -- 5.8 U ------5.8 U 58 U 5.8 U 58 U 5.8 U 73.5 Heptanoic acid mg/L 6.6 6.6 U -- 6.6 U ------6.6 U 66 U 6.6 U 66 U 6.6 U 66 U
Notes: Q = Laboratory qualifier µg/L = micrograms per liter U = Below detection limit (reporting limit shown) mg/L = milligrams per liter J = Estimated value µS/cm = microSiemens per centimeter NR = Not reported su = standard units 1 Red font - validation qualifiers = units are mg/L as CaCO3 T = Total Fraction NA = Not Applicable D = Dissolved Fraction -- = Not analyzed
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1 Table A2 DQIs and Corresponding QC Parameters DQIs QC Parameters Evaluated in Data Review/Validation Precision Relative Percent Difference (RPD) values of: 1) LCS/ Laboratory Control Sample Duplicate (LCSD) 2) MS/MSD Relative Percent Difference (RPD) 3) Field duplicates Accuracy/Bias Percent Recovery (%R) or Percent Difference (%D) values of: 1) Initial calibration and continuing calibration verification 2) LCS/LCSD 3) MS/MSD Results of: 1) Instrument and calibration blanks 2) Method (preparation) blanks Representativeness Sample integrity (Chain‐of Custody and sample receipt forms) Holding times Comparability Sample‐specific reporting limits (RLs) Sample collection methods Laboratory analytical methods Completeness Data qualifiers Laboratory deliverables Requested/reported valid results Field sample collection (primary and QC samples) Contract compliance (i.e., method and instrument QC within limits) Sensitivity Method Reporting Limits (MRLs) Adequacy of sample dilution
Page 1 of 1 Formosa Mine Superfund Site OU2, Douglas County, Oregon Table A3 CLP / ORD Data Comparison Sampling Event #5 Total Metals (µg/L) Blank BCR1 BCR2 BCR3 BCR4 BCR5 BCR6 Chitorem Pretreat SAPS Pretreat Adit Adit Dup MJGB20 MJGB18 MJGB22 MJGB24 MJGB26 MJGB28 MJGB30 MJGB32 MJGB34 MJGB36 MJGB38 CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD Aluminum 200 UJ 105 U 5660 J 1,720 106.8 26.8 J 105 U 39.0 J 105 U 25.7 J 105 U 73.9 J 105 U 200 UJ 105 U 200 UJ 105 U 2060 J 2,420 16.1 10900 J 12,600 14.5 12100 J 12,600 4.0 Antimony 60.0 U 106 U 60.0 U 106 U 60.0 U 106 U 60.0 U 106 U 60.0 U 106 U 60.0 U 106 U 60.0 U 106 U 60.0 U 106 U 60.0 U 106 U 60.0 U 106 U 60 U 106 U Arsenic 10.0 U 40 U 10.0 U 40 U 10.0 U 40 U 10.0 U 40 U 10.0 U 40 U 10.0 U 40 U 28.6 40 33.2 10.0 U 40 U 10.0 U 40 U 31.0 51 48.8 33.8 51 40.6 Barium 3.4 J 17 U 69.0 J 144 70.4 161 J 206 24.5 138 J 157 12.9 146 J 210 36.0 93.1 J 146 44.2 304 259 16.0 80.1 J 97 19.1 49.5 J 56 12.3 200 U 17 U 200 U 17 U Beryllium 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5U‐‐ Cadmium 5.0 UJ 3 U 28.4 J 32 11.9 5.0 UJ 3 U 5.0 UJ 3 U 5.0 UJ 3 U 5.0 UJ 3 U 5.0 UJ 3 U 5.0 UJ 3 U 26.0 J 25 3.9 133 J 136 2.2 138 J 137 0.7 Calcium 47.5 J 285 U 188000 J 201,000 6.7 602000 J 703,000 15.5 248000 J 242,000 2.4 582000 J 764,000 27.0 263000 J 303,000 14.1 852000 J 943,000 10.1 213000 J 212,000 0.5 181000 J 186,000 2.7 99000 J 106,000 6.8 109000 J 107,000 1.9 Chromium 10.0 U 24 U 10.0 U 85 10.0 U 24 U 10.0 U 26 10.0 U 24 U 10.0 U 24 U 10.0 U 24 U 10.0 U 24 U 10.0 U 127 10.0 U 155 10 U 154 Cobalt 50.0 U 11 U 6.1 J 20 106.5 3.1 J 11 U 50.0 U 11 U 50.0 U 11 U 0.66 J 11 U 3.3 J 11 U 50.0 U 11 U 10.4 J 13 22.2 9.7 J 13 29.1 9.7 J 12 21.2 Copper 25.0 UJ 8 U 601 J 108 139.1 25.0 UJ 8 25.0 UJ 30 25.0 UJ 8 UU 22.2 J 67 100.4 25.0 UJ 8 U 25.0 UJ 12 70.3 166 J 187 11.9 3250 J 3570 9.4 3580 J 3590 0.3 Iron 100 UJ 122 97700 J 97300 0.4 6250 J 6970 10.9 30600 J 33700 9.6 6510 J 4940 27.4 1090 J 2580 81.2 2420 J 2530 4.4 11500 J 13300 14.5 122000 J 131000 7.1 144000 J 158000 9.3 159000 J 158000 0.6 Lead 10.0 U 19 U 10.5 19 U 10.0 U 19 U 10.0 U 19 U 10.0 U 19 U 10.0 U 19 U 10.0 U 19 U 10.0 U 19 U 10.0 U 19 U 31.2 19 U 30.5 19 U Magnesium 5000 UJ 11 U 26800 J 30000 11.3 37500 J 47900 24.4 26600 J 30200 12.7 39400 J 55900 34.6 27000 J 36000 28.6 69800 J 80200 13.9 25800 J 30500 16.7 24500 J 26500 7.8 22500 J 24800 9.7 24900 J 24900 0.0 Manganese 15.0 UJ 16 U 2250 J 2670 17.1 510 J 668 26.8 2490 J 2810 12.1 1350 J 1560 14.4 988 J 1340 30.2 580 J 735 23.6 1220 J 1440 16.5 2230 J 2390 6.9 1890 J 2090 10.1 2090 J 2100 0.5 Mercury 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ Nickel 40.0 U 5 U 34.7 J 20 53.7 6.0 J 6 0.0 40.0 U 5 U 4.6 J 7 41.4 4.9 J 6 20.2 14.7 J 16 8.5 1.4 J 5 U 55.8 37 40.5 54.8 33 49.7 56.9 33 53.2 Potassium 5000 U 945 U 5000 U 3510 5000 U 6670 28.6 5000 U 3570 5590 10600 61.9 5080 8100 45.8 14200 17400 20.3 5000 U 3130 46.0 5000 U 2500 5000 U 2030 84.5 5000 U 2140 80.1 Selenium 35.0 U ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 9.0 J ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 35 U ‐‐ Silver 10.0 U 3 U 8.0 J 3 U 0.67 J 3 U 2.6 J 3 U 10.0 U 3 U 10.0 U 3 U 10.0 U 3 U 1.1 J 3 U 10.5 3 U 12.5 3 U 14.3 3 U Sodium 5000 U 1520 U 9980 13800 32.1 18200 23200 24.2 8860 9940 11.5 12000 15100 22.9 15400 19200 22.0 32800 37600 13.6 11200 12700 12.6 9200 9800 6.3 8850 9810 10.3 9760 9500 2.7 Thallium 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25 U ‐‐ Vandium 50.0 U 29 U 50.0 U 29 U 50.0 U 29 U 50.0 U 29 U 50.0 U 29 U 50.0 U 29 U 50.0 U 29 U 50.0 U 29 U 50.0 U 29 U 6.1 J 29 U 6.5 J 29 U Zinc 11.6 J 7 49.5 26300 J 28700 8.7 60.0 U 35 2110 J 2580 20.0 66.9 J 90 29.4 166 J 519 103.1 60.0 U 34 55.3 60.0 U 26 79.1 47100 J 57300 19.5 54200 J 64100 16.7 56900 J 65400 13.9 General Chemistry (mg/L) Alkalinity 5 U 63 5U125 2360 3440 37.2 197 250 23.7 1720 2880 50.4 1230 1630 28.0 3810 6000 44.6 888 1310 38.4 5 U 63 5U5U 5U5U Sulfide 0.01 U 0.01 U 1 0.16 200 125 11.0 Fluoride 0.04 U 0.022 U 1.07 1.58 38.3 2 U 0.222 U 0.872 1.20 31.3 2 U 0.222 U 2 U 0.64 2 U 0.222 U 2 U 1.08 1.2 2.07 53.1 1.54 2.07 29.3 1.55 1.47 5.0 Chloride 0.06 U 0.114 U 3.17 4.04 24.1 8.53 5.10 50.3 3.07 3.14 2.3 3.35 1.54 74.0 7.27 7.29 0.3 3.62 7.03 64.1 4.04 3.91 3.2 3.16 3.59 12.8 3.16 3.75 17.1 3.13 3.20 2.3 Sulfate 0.3 U 0.331 U 667 1400 70.9 3.22 3.31 U 580 610 5.0 249 222 11.3 20.5 30.3 38.6 2.81 3.31 U 21.7 38.5 55.7 778 1003 25.3 806 2004 85.2 817 2304 95.3 Dissolved Metals (µg/L) MJGB21 MJGB19 MJGB23 MJGB25 MJGB27 MJGB29 MJGB31 MJGB33 MJGB35 MJGB37 MJGB39 CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD RPD CLP ORD CLP ORD RPD CLP ORD RPD CLP ORD RPD Aluminum 200 U 95 U 1340 1,550 14.5 200 U 95 U 28.2 J 95 U 200 U 95 U 200 U 95 U 200 U 95 U 200 U 95 U 435 466 6.9 11900 12,400 4.1 11900 12400 4.1 Antimony 60.0 U 95 U 60.0 U 95 U 60.0 U 95 U 60.0 U 95 U 60.0 U 95 U 60.0 U 95 U 60.0 U 95 U 60.0 U 95 U 60.0 U 95 U 60.0 U 95 U 60.0 U 95 U Arsenic 10.0 U 36 U 10.0 U 36 U 10.0 U 36 U 10.0 U 36 U 10.0 U 36 U 10.0 U 36 U 20.7 45 74.0 10.0 U 36 U 10.0 U 36 U 15.0 39 88.9 15.6 39 85.7 Barium 200 U 517 64.6 J 130 67.2 148 J 562 116.6 144 J 132 8.7 148 J 382 88.3 91.0 J 659 151.5 274 755 93.5 66.1 J 652 163.2 53.5 J 177 107.2 9.7 J 243 184.6 11.8 J 108 160.6 Beryllium 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ 5.0 U ‐‐ Cadmium 5.0 U 2 U 23.7 29 20.1 5.0 U 2 U 5.0 U 2 U 5.0 U 2 U 5.0 U 2 U 5.0 U 2 U 5.0 U 2 U 28.0 32 13.3 137 142 3.6 136 141 3.6 Calcium 51.1 J 257 U 176000 181,000 2.8 770000 766,000 0.5 260000 238,000 8.8 594000 603,000 1.5 267000 286,000 6.9 790000 924,000 15.6 201000 208,000 3.4 181000 176,000 2.8 107000 102,000 4.8 106000 102000 3.8 Chromium 10.0 U 22 U 10.0 U 77 10.0 U 22 U 10.0 U 27 10.0 U 22 U 10.0 U 22 U 10.0 U 22 U 10.0 U 22 U 10.0 U 89 10.0 U 112 10.0 U 113 Cobalt 50.0 U 10 U 4.6 J 18 118.6 3.7 J 10 U 50.0 U 10 U 0.81 J 10 U 50.0 U 10 U 2.6 J 10 U 50.0 U 10 U 10.3 J 20 64.0 9.9 J 19 63.0 9.7 J 19 64.8 Copper 25.0 U 7 U 5.4 J 98 179.1 25.0 U 7 U 25.0 U 108 25.0 U 7 U 25.0 U 7 U 25.0 U 7 U 25.0 U 8 86.3 209 83.1 3540 3830 7.9 3520 3800 7.7 Iron 100 U 111 85100 87600 2.9 4610 517 159.7 33900 31600 7.0 4140 2750 40.3 162 173 6.6 1350 1160 15.1 10100 10400 2.9 121000 121000 0.0 156000 150000 3.9 157000 150000 4.6 Lead 10.0 U 17 U 10.0 U 17 U 10.0 U 17 U 10.0 U 17 U 10.0 U 17 U 10.0 U 17 U 10.0 U 17 U 10.0 U 17 U 10.0 U 17 U 29.8 17 U 29.7 17 U Magnesium 5000 U 17 24300 27000 10.5 47300 48700 2.9 27900 28000 0.4 40500 44500 9.4 27400 33000 18.5 65700 76100 14.7 24900 28500 13.5 24700 26500 7.0 24300 25400 4.4 24500 25300 3.2 Manganese 15.0 U 14 U 2080 2404 14.5 590 648 9.4 2600 2740 5.2 1460 1640 11.6 974 1200 20.8 550 679 21.0 1130 1370 19.2 2210 2360 6.6 2060 2100 1.9 2020 2110 4.4 Mercury 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ 0.21 ‐‐ 0.2 U ‐‐ 0.2 U ‐‐ Nickel 0.47 J 4 U 28.1 J 18 43.8 40.0 UJ 6 40.0 UJ 4 U 40.0 UJ 5 40.0 UJ 4 40.0 UJ 14 40.0 UJ 4 U 53.9 J 37 37.2 56.5 J 33 52.5 55.3 J 33 50.5 Potassium 5000 U 852 U 5000 U 3160 5210 7150 31.4 5000 U 3910 5690 7640 29.3 5130 7830 41.7 12800 17000 28.2 5000 U 3600 5000 U 2730 5000 U 2530 5000 U 2470 Selenium 35.0 U ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 4.7 J ‐‐ 35.0 U ‐‐ 10.3 J ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ 35.0 U ‐‐ Silver 10.0 U 3 U 7.6 J 3 U 10.0 U 3 U 3.3 J 3 U 3 U 10.0 U 3 U 10.0 U 3 U 10.0 U 3 U 1.6 J 3 U 11.0 3 U 13.7 3 U 14.0 3 U Sodium 5000 U 1710 9020 12400 31.6 22500 26400 16.0 9380 11800 22.9 12500 15700 22.7 15300 20600 29.5 29300 37200 23.8 10800 14700 30.6 9200 12600 31.2 9670 13000 29.4 9920 13100 27.6 Thallium 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ 25.0 U ‐‐ Vandium 50.0 U 26 U 50.0 U 26 U 50.0 U 26 U 50.0 U 26 U 50.0 U 26 U 50.0 U 26 U 50.0 U 26 U 50.0 U 26 U 50.0 U 26 U 6.0 J 26 U 50.0 U 26 U Zinc 60.0 U 305 22100 26100 16.6 60.0 U 241 421 667 45.2 60.0 U 260 10.6 J 307 186.6 9.8 J 220 182.9 60.0 U 313 45000 56700 23.0 56400 65100 14.3 57000 61500 7.6
Notes: All results in units of ug/L U = not detected All results shown are normal field samples (no field duplicates) J = estimated Q = qualifer Bold = RPD exceeds 100%
Formosa Mine Superfund Site OU2, Douglas County, Oregon Page 1 of 1