i ii Ambient Groundwater Quality of the Upper Hassayampa Basin: A 2003-2009 Baseline Study By Douglas C. Towne Maps by Jean Ann Rodine Arizona Department of Environmental Quality Open File Report 13-03 ADEQ Water Quality Division Surface Water Section Monitoring Unit 1110 West Washington St. Phoenix, Arizona 85007-2935 Thanks: Field Assistance: Elizabeth Boettcher, Angela Lucci, Brent Mitchell, and Meghan Smart. Special recognition is extended to the many well owners who were kind enough to give permission to collect groundwater data on their property. Photo Credits: Douglas Towne Report Cover: An unused aqueduct, the Leppe Wash flume, is located on the historic TK Bar Ranch along the Hassayampa River near Kirkland, Arizona. The inset photo shows the ML Windmill, the water tank of which also serves as a sign post along the rugged Wagoner Road that connects the communities of Kirkland Junction and Crown King. The cover collage was created by Phil Amorosi and Nancy Caroli. iii Other Publications of the ADEQ Ambient Groundwater Monitoring Program ADEQ Ambient Groundwater Quality Open-File Reports (OFR) and Factsheets (FS): Upper Hassayampa Basin OFR 13-03, 52 p. FS 13-11, 4 p. Aravaipa Canyon Basin OFR 13-01, 46 p. FS 13-04, 4 p. Butler Valley Basin OFR 12-06, 44 p. FS 12-10, 5.p. Cienega Creek Basin OFR 12-02, 46 p. FS 12-05, 4.p. Ranegras Plain Basin OFR 11-07, 63 p. FS 12-01, 4.p. Groundwater Quality in Arizona OFR 11-04, 26 p. - Bill Williams Basin OFR 11-06, 77 p. FS 12-01, 4.p. San Bernardino Valley Basin OFR 10-03, 43 p. FS 10-31, 4 p. Dripping Springs Wash Basin OFR 10-02, 33 p. FS 11-02, 4 p. McMullen Valley Basin OFR 11-02, 94 p. FS 11-03, 6 p. Gila Valley Sub-basin OFR 09-12, 99 p. FS 09-28, 8 p. Agua Fria Basin OFR 08-02, 60 p. FS 08-15, 4 p. Pinal Active Management Area OFR 08-01, 97 p. FS 07-27, 7 p. Hualapai Valley Basin OFR 07-05, 53 p. FS 07-10, 4 p. Big Sandy Basin OFR 06-09, 66 p. FS 06-24, 4 p. Lake Mohave Basin OFR 05-08, 66 p. FS 05-21, 4 p. Meadview Basin OFR 05-01, 29 p. FS 05-01, 4 p. San Simon Sub-Basin OFR 04-02, 78 p. FS 04-06, 4 p. Detrital Valley Basin OFR 03-03, 65 p. FS 03-07, 4 p. San Rafael Basin OFR 03-01, 42 p. FS 03-03, 4 p. Lower San Pedro Basin OFR 02-01, 74 p. FS 02-09, 4 p. Willcox Basin OFR 01-09, 55 p. FS 01-13, 4 p. Sacramento Valley Basin OFR 01-04, 77 p. FS 01-10, 4 p Upper Santa Cruz Basin (w/ USGS) OFR 00-06, 55 p. - Prescott Active Management Area OFR 00-01, 77 p. FS 00-13, 4 p. Upper San Pedro Basin (w/ USGS) OFR 99-12, 50 p. FS 97-08, 2 p. Douglas Basin OFR 99-11, 155 p. FS 00-08, 4 p. Virgin River Basin OFR 99-04, 98 p. FS 01-02, 4 p. Yuma Basin OFR 98-07, 121 p. FS 01-03, 4 p. These publications are available at: www.azdeq.gov/environ/water/assessment/ambient.html iv Map 1. ADEQ Ambient Groundwater Monitoring Program Studies v Table of Contents Abstract .................................................................................................................................................................... 1 Introduction ............................................................................................................................................................. 2 Purpose and Scope ...................................................................................................................................... 2 Physical and Cultural Characteristics .......................................................................................................... 2 Surface Water Characteristics ..................................................................................................................... 2 Groundwater Characteristics ....................................................................................................................... 4 Investigation Methods ............................................................................................................................................. 4 Sample Collection ....................................................................................................................................... 4 Laboratory Methods .................................................................................................................................... 9 Data Evaluation ....................................................................................................................................................... 9 Quality Assurance ....................................................................................................................................... 9 Data Validation ......................................................................................................................................... 12 Statistical Considerations .......................................................................................................................... 15 Groundwater Sampling Results ........................................................................................................................... 16 Water Quality Standards / Guidelines ....................................................................................................... 16 Suitability for Irrigation ............................................................................................................................ 16 Analytical Results .................................................................................................................................... 16 Groundwater Composition ................................................................................................................................... 23 General Summary .................................................................................................................................... .23 Constituent Co-Variation .......................................................................................................................... 28 Oxygen and Hydrogen Isotopes ................................................................................................................ 30 Groundwater Quality Variation ................................................................................................................ 32 Discussion ............................................................................................................................................................... 40 References .............................................................................................................................................................. 41 Appendices Appendix A – Data for Sample Sites, Upper Hassayampa Basin, 2003-2009 .......................................... 43 Appendix B – Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009 ................................... 45 vi Maps ADEQ Ambient Monitoring Program Studies .......................................................................................................... V Map 1. Upper Hassayampa Basin ........................................................................................................................... 3 Map 2. Sample Sites ................................................................................................................................................ 5 Map 3. Water Quality Standards ............................................................................................................................ 17 Map 4. Radon ......................................................................................................................................................... 18 Map 5. Water Chemistry ........................................................................................................................................ 24 Map 6. Total Dissolved Solids ............................................................................................................................... 26 Map 7. Hardness .................................................................................................................................................... 27 Map 8. Isotope ....................................................................................................................................................... 31 Map 9. Hardness .................................................................................................................................................... 33 Map 10. Isotope ..................................................................................................................................................... 37 Tables Table 1. Laboratory water methods and minimum reporting levels used in the study .......................................... 10 Table 2. Summary results of duplicate samples from the ADHS laboratory ....................................................... 13 Table 3. Summary results of split samples between the ADHS/Test America labs .............................................. 14 Table 4. Sampled sites exceeding health-based water quality guidelines or Primary MCLs ................................ 19 Table 5. Sampled sites exceeding aesthetics-based water quality guidelines or Secondary MCLs ...................... 20 Table 6. Sodium and salinity hazards for sampled sites........................................................................................ 20 Table 7. Summary statistics for groundwater quality data .................................................................................... 21 Table 8. Correlation among groundwater quality constituent concentrations ....................................................... 29 Table 9. Variation in groundwater quality constituent concentrations between two recharge groups .................. 34 Table 10. Summary statistics for two recharge groups with significant constituent differences .......................... 35 Table 11. Variation in groundwater quality constituent concentrations between two geologic groups ................ 38 Table 12. Summary statistics for two geologic groups with significant constituent differences .......................... 39 vii Diagrams Diagram 1. pH-field – pH-lab relationship .......................................................................................................... 15 Diagram 2. Water chemistry piper plot ................................................................................................................ 23 Diagram 3. Hardness concentrations .................................................................................................................... 25 Diagram 4. Bicarbonate – hardness relationship ................................................................................................. 28 Diagram 5. Oxygen-18 – deuterium relationship ................................................................................................ 30 Diagram 6. Sodium box plot using two recharge groups...................................................................................... 32 Diagram 7. Fluoride box plot using two recharge groups .................................................................................... 32 Diagram 8. Nitrate box plot using two geologic groups ....................................................................................... 35 Diagram 9. pH-field box plot using two geologic groups .................................................................................... 35 Figures Figure 1. Diamond Two Ranch House Well ......................................................................................................... 6 Figure 2. Sinoski Spring ........................................................................................................................................ 6 Figure 3. Hassayampa River at Wagoner Road ..................................................................................................... 7 Figure 4. Upper Oak Creek Windmill .................................................................................................................... 7 Figure 5. Senator Spring ........................................................................................................................................ 7 Figure 6. Collins Spring ......................................................................................................................................... 7 Figure 7. Leppe Wash Flume ................................................................................................................................. 8 Figure 8. Parker Dairy Farm Well ......................................................................................................................... 8 Figure 9. Wells near Groom Creek ........................................................................................................................ 8 Figure 10. TK Bar Ranch Well #1 ........................................................................................................................... 8 viii Abbreviations amsl ac-ft af/yr ADEQ ADHS ADWR ARRA AZGS As bls BLM CAP o C CI0.95 Cl EPA F Fe gpm GWPL HCl LLD Mn MCL ml msl ug/L um uS/cm mg/L MRL ns ntu pCi/L QA QAPP QC SAR SDW SC su SO4 TDS TKN UHA USFS USGS VOC WQARF * ** *** above mean sea level acre-feet acre-feet per year Arizona Department of Environmental Quality Arizona Department of Health Services Arizona Department of Water Resources Arizona Radiation Regulatory Agency Arizona Geological Survey arsenic below land surface U.S. Department of the Interior Bureau of Land Management Central Arizona Project degrees Celsius 95 percent Confidence Interval chloride U.S. Environmental Protection Agency fluoride iron gallons per minute Groundwater Protection List active ingredient hydrochloric acid Lower Limit of Detection manganese Maximum Contaminant Level milliliter mean sea level micrograms per liter micron microsiemens per centimeter at 25° Celsius milligrams per liter Minimum Reporting Level not significant nephelometric turbidity unit picocuries per liter Quality Assurance Quality Assurance Project Plan Quality Control Sodium Adsorption Ratio Safe Drinking Water Specific Conductivity standard pH units sulfate Total Dissolved Solids Total Kjeldahl Nitrogen Upper Hassayampa Groundwater Basin U.S. Forest Service U.S. Geological Survey Volatile Organic Compound Water Quality Assurance Revolving Fund significant at p ≤ 0.05 or 95% confidence level significant at p ≤ 0.01 or 99% confidence level for information only, statistical test for this constituent invalid because detections fewer than 50 percent ix x Ambient Groundwater Quality of the Upper Hassayampa Basin: A 2003-2009 Baseline Study Abstract - From 2003-2009, the Arizona Department of Environmental Quality conducted a baseline groundwater quality study of the Upper Hassayampa basin located approximately 60 miles northwest of Phoenix. The basin comprises 787 square miles within Maricopa and Yavapai counties and had an estimated population of 10,479 in 2000.4 The largest population center in the basin is the Town of Wickenburg; other communities include Congress, Groom Creek, and Wagoner. The basin is characterized by mid-elevation mountains and valleys. Low-intensity livestock grazing is the predominant land use and ranches sometimes have limited acreages of irrigated pasture for additional feed. The basin contains a large inactive copper mine, the Zonia Property located northwest of Wagoner.4 Land ownership in the basin consists of federal lands (46 percent) managed by the U.S. Forest Service (25 percent) and the Bureau of Land Management (21 percent), State Trust lands (38 percent), and private land (16 percent). 3 The basin is drained by the Hassayampa River, a tributary to the Gila River, which begins in the Bradshaw Mountains. The stream flows south until exiting the basin about five miles south of Wickenburg. The Hassayampa River is mostly intermittent but is perennial in its upper reaches and south of Wickenburg; some of its tributaries also have limited perennial stretches.4 There are no surface water diversions or impoundments besides stock ponds within the basin as groundwater is used for all public water supply, domestic, irrigation, and industrial uses. Groundwater occurs primarily in the basin-fill aquifer that is generally found in the southeastern portion of the basin. Composed of gravel, sand, silt, and clay, the basin-fill aquifer can yield up to several hundred gallons per minute. Smaller alluvial deposits are also found in valleys particularly along the Hassayampa River in the northcentral portion of the basin. Lesser amounts of groundwater are found in the surrounding bedrock, especially along faults, fracture zones, and/or localized perched aquifers.4,19 Most groundwater is used for public water supply, irrigation, and industrial (primarily dairy) uses; only minor amounts are used for stock and domestic purposes.4 Thirty-four sites (27 wells and 7 springs) were sampled for the study. Inorganic constituents and isotopes (oxygen and deuterium) were collected at each site while radon (17) and radionuclide (12) were collected at selected sites. Based on these water quality sample results, groundwater in the basin is generally suitable for drinking water uses. Of the 34 sites sampled, 20 sites met all drinking water quality standards not including the proposed radon standard. Health-based, Primary Maximum Contaminant Levels (MCLs) were exceeded at nine sites (27 percent). These enforceable standards define the maximum concentrations of constituents allowed in water supplied for drinking water purposes by a public water system and are based on a lifetime daily consumption of two liters. 25 Constituents exceeding Primary MCLs include arsenic (1 site), gross alpha (5 sites), and nitrate (4 sites). Aesthetics-based, Secondary MCLs were exceeded at 13 of the 34 sites (38 percent). These are unenforceable guidelines that define the maximum constituent concentration that can be present in drinking water without an unpleasant taste, color, or odor.25 Constituents exceeding Secondary MCLs include chloride (1 site), fluoride (4 sites), iron (2 sites), manganese (4 sites), sulfate (1 site), and Total Dissolved Solids (TDS) (8 sites). Of the 17 sites sampled for radon, none exceeded the proposed 4,000 picocuries per liter (pCi/L) standard while 8 sites (47 percent) exceeded the proposed 300 pCi/L standard. 25 Groundwater in the basin typically has calcium or mixed-bicarbonate chemistry and is slightly-alkaline, fresh, and hard to very hard, based on pH levels along with TDS and hardness concentrations.8, 11 Oxygen and deuterium isotope values at most sites appear to reflect the elevation at which the sample sites were located. Five samples that were depleted experienced little evaporation and are located in the Bradshaw Mountains. The other 29 samples were more enriched, suggesting the water from these lower elevation sites was subject to much greater evaporation.9 Groundwater constituent concentrations were influenced by recharge group and geology.9, 16 Constituents such as temperature, pH-lab, sodium, potassium, chloride, fluoride, oxygen-18 and deuterium had significantly higher constituent concentrations at sites with enriched samples collected at lower elevations than at sites with depleted samples collected at higher elevations. (Kruskal-Wallis test, p ≤ 0.05). Constituents such as temperature, sodium, sulfate, nitrate, fluoride, and deuterium had significantly greater concentrations in sites located in unconsolidated sediments than in consolidated rock; turbidity had the opposite pattern (Kruskal-Wallis test, p ≤ 0.05). 1 INTRODUCTION Purpose and Scope The Upper Hassayampa groundwater basin (UHA) comprises approximately 787 square miles within Maricopa and Yavapai counties (Map 1).4 The basin is located about 60 miles northwest of Phoenix and includes the Town of Wickenburg and the communities of Congress, Groom Creek, and Wagoner. The basin is drained by the Hassayampa River which heads in the Bradshaw Mountains in the extreme northern part of the basin and flows south until exiting the basin about five miles south of Wickenburg. There are no surface water diversions or impoundments besides stock ponds within the basin as groundwater is used for all municipal, domestic, irrigation, and industrial uses.4 Sampling by the Arizona Department of Environmental Quality (ADEQ) Ambient Groundwater Monitoring program is authorized by legislative mandate in the Arizona Revised Statutes §49-225, specifically: “...ongoing monitoring of waters of the state, including...aquifers to detect the presence of new and existing pollutants, determine compliance with applicable water quality standards, determine the effectiveness of best management practices, evaluate the effects of pollutants on public health or the environment, and determine water quality trends.” 2 Benefits of ADEQ Study – This study, which utilizes scientific sampling techniques and quantitative analyses, is designed to provide the following benefits: • A characterization of regional groundwater quality conditions in the Upper Hassayampa basin identifying water quality variations between groundwater originating from different sources. • A process for evaluating potential groundwater quality impacts arising from mineralization, mining, livestock, septic tanks, and poor well construction. • A guide for determining areas where further groundwater quality research is needed. Physical and Cultural Characteristics Geography – The Upper Hassayampa basin is located within the Central highlands physiographic province of central Arizona and contains relatively small basins with alluvial deposits. The basin is characterized by mid-elevation mountains and valleys. Vegetation is composed of Arizona upland Sonoran and Mohave desert scrub, semi-desert grassland, interior chaparral, and limited montane conifer forest. Riparian vegetation includes mesquite, cottonwood, and willow found along perennial stretches of the Hassayampa River. 4 The basin is bounded on the north by the Weaver Mountains, on the northwest by the Date Creek Mountains, on the south by the Vulture Mountains, and on the east by the Bradshaw Mountains. Elevations in the basin range from a high of approximately 7,000 feet above mean sea level (amsl) in the Bradshaw Mountains to a low of approximately 1,900 feet amsl at the railroad siding of Allah where the Hassayampa River exits the basin into the Phoenix Active Management Area. The Upper Hassayampa basin consists of federal land (46 percent) managed by the U.S. Forest Service (USFS) (25 percent) Bureau of Land Management (BLM) (21 percent). The remainder of the basin is composed of State Trust land (38 percent) and private land (16 percent).3 Generally, USFS lands are located in the northeast portion, BLM lands are in the central portion, and State Trust and private land is interspersed throughout the southern two-thirds of the basin (Map 2). Climate – The Upper Hassayampa basin is in an arid climate characterized by hot, dry summers and mild winters. There is wide variation in precipitation amounts which range annually from 10 inches in the southern portion near Wickenburg to 32 inches in the highest elevations of the Bradshaw Mountains. Precipitation occurs predominantly as rain in either late summer, localized thunderstorms or, less often, as widespread, low intensity winter rain that includes snow at higher elevations. 4 Surface Water Characteristics The basin is drained by the Hassayampa River, a tributary to the Gila River, which flows from north to south in the basin. The river is intermittent but has perennial flow in its upper reach and also in the extreme lower reach where groundwater is brought to the surface by bedrock south of Wickenburg. The Hassayampa River has a mean annual flow of 17,585 acre-feet at Box Dam site near Wickenburg. Perennial flow is also found in the upper reaches of Antelope Creek, Ash Creek, Weaver Creek, and Minnehaha Creek. Average seasonal flow is usually highest in the winter and lowest in the fall. 4 2 3 Groundwater Characteristics Groundwater occurs primarily in the basin-fill aquifer, which is generally found in the southeast portion of the basin. The basin-fill aquifer is composed of gravel, sand, silt, and clay and may yield several hundred gallons per minute. In the main alluvial basin north of the Vulture Mountains, the basin-fill ranges from 25 feet thick to over 1,000 feet thick toward the center of the deposits. 4 In the northern portion of the basin, smaller alluvial deposits may also be found in valleys. In some areas along the Hassayampa River, the crystalline rock is overlain by a thin cover of stream deposits that are up to 135 feet thick. Groundwater is also found in limited amounts in the consolidated crystalline and sedimentary rocks that make up the majority of the basin. 19 Groundwater flows generally from north to south. Depth to groundwater varies significantly across the basin from just a few feet below land surface (bls) along some stretches of the Hassayampa River to over 1,000 feet bls in the center of the basin. Natural recharge estimates for the basin is 8,000 acre-feet per year while groundwater use is estimated to be 3,900 af/yr. Total estimated recoverable groundwater in storage in the basin-fill sediments to a depth of 1,200 feet bls is estimated around 1.0 million acre-feet (af). 4,19 permission to sample, a sampling point existed near the wellhead, and the well casing and surface seal appeared to be intact and undamaged.1, 5 For this study, ADEQ personnel sampled 20 wells served by submersible pumps, 6 windmills, and 1 monitoring well. The wells were primarily used for domestic and/or stock use. Seven springs were also sampled that were primarily used for stock watering. Additional information on groundwater sample sites is compiled from the Arizona Department of Water Resources (ADWR) well registry in Appendix A. 4 Sample Collection The sample collection methods for this study conformed to the Quality Assurance Project Plan (QAPP)1 and the Field Manual for Water Quality Sampling.5 While these sources should be consulted as references to specific sampling questions, a brief synopsis of the procedures involved in collecting a groundwater sample is provided. After obtaining permission from the well owner, the volume of water needed to purge the well three borehole volumes was calculated from well log and on-site information. Physical parameters—temperature, pH, and specific conductivity—were monitored at least every five minutes using a YSI multi-parameter instrument. INVESTIGATION METHODS ADEQ collected samples from 34 sites to characterize regional groundwater quality in the Upper Hassayampa basin (Map 2). Specifically, the following types of samples were collected: • • • • oxygen and deuterium isotopes at 34 sites inorganic suites at 34 sites radon at 17 sites radionuclides at 12 sites In addition, four surface water isotope samples were collected; three from Hassayampa River and one from Minnehaha Creek. No bacteria sampling was conducted because microbiological contamination problems in groundwater are often transient and subject to a variety of changing environmental conditions including soil moisture content and temperature. 10 Wells pumping groundwater for domestic, stock, irrigation, and monitoring purposes were sampled for the study, provided each well met ADEQ requirements. A well was considered suitable for sampling when the following conditions were met: the owner has given To assure obtaining fresh water from the aquifer, after three bore volumes had been pumped and physical parameter measurements had stabilized within 10 percent, a sample representative of the aquifer was collected from a point as close to the wellhead as possible. In certain instances, it was not possible to purge three bore volumes. In these cases, at least one bore volume was evacuated and the physical parameters had stabilized within 10 percent. Sample bottles were filled in the following order: 1. 2. 3. 4. Radon Inorganics Radionuclide Isotopes Radon, a naturally occurring, intermediate breakdown from the radioactive decay of uranium-238 to lead-206, was collected in two unpreserved, 40 milliliter (ml) clear glass vials. Radon samples were filled to minimize volatilization and sealed so that no headspace remained.5, 20 4 5 Figure 1 – The Diamond Two Ranch house well used for domestic purposes was sampled (UHA-35) for the ADEQ study. Analytical results indicated the water met all drinking water quality standards. Figure 2 – Sinoski Spring used for livestock and wildlife purposes was sampled (UHA-10) for the ADEQ study. Analytical results indicated the water met all drinking water quality standards. 6 Figure 3 – Intermittent flow in the Hassayampa River at the Wagoner Road Bridge; the stream is perennial at higher and lower elevations in the basin. Figure 5 – ADEQ’s Meghan Smart collects a sample (UHA-26) from Senator Spring located high in the Bradshaw Mountains along the road to Crown King. Figure 4 – ADEQ’s Douglas Towne stretches to collect a sample (UHA-28) from the Upper Oak Creek windmill. The water, which is used for livestock and wildlife, met all Primary and Secondary standards. Figure 6 – ADEQ’s Elizabeth Boettcher collects a sample (UHA-31) from Collins Spring located in the Prescott National Forest. Analytical results indicated the Secondary MCL for manganese was exceeded. 7 Figure 9 – Greg Norris, John Rebb, his wife, Sandy, and ADEQ’s Elizabeth Boettcher pose for a photo after collecting samples (UHA-12 and UHA-13) from two wells near the top of the Upper Hassayampa basin by Groom Creek. Analytical results from both samples met all water quality standards. Figure 7 – An unused aqueduct, the Leppe Wash flume, is located on the historic TK Bar Ranch along the Hassayampa River near Kirkland, Arizona. Figure 8 – ADEQ’s Douglas Towne samples the well that serves Parker Dairy Farm located northwest of the town of Congress. Analytical results from the sample (UHA-11) indicated water from the 1,050-foot well exceeded water quality standards for TDS, nitrate, and gross alpha. Figure 10 – The 300-foot TK Bar Ranch Well #1 is shown pumping into a river-rock lined ditch. Nearby is the 500-foot TK Bar Ranch Well #2 that has artesian flow. Samples (UHA-37 and UHA-38) from both wells met all water quality standards. 8 The inorganic constituents were collected in three, one-liter polyethylene bottles: samples to be analyzed for dissolved metals were delivered to the laboratory unfiltered and unpreserved where they were subsequently filtered into bottles using a positive pressure filtering apparatus with a 0.45 micron (µm) pore size groundwater capsule filter and preserved with 5 ml nitric acid (70 percent). Samples to be analyzed for nutrients were preserved with 2 ml sulfuric acid (95.5 percent). Samples to be analyzed for other parameters were unpreserved.5, 17, 20 Radiochemistry samples were collected in two collapsible four-liter plastic containers and preserved with 5 ml nitric acid to reduce the pH below 2.5 su. 5 Oxygen and hydrogen isotope samples were collected in a 250 ml polyethylene bottle with no preservative.5, 24 All samples were kept at 4°C with ice in an insulated cooler, with the exception of the oxygen and hydrogen isotope samples.5,17,20 Chain of custody procedures were followed in sample handling. Samples for this study were collected during eight field trips conducted between 2003 and 2009. Laboratory Methods The inorganic analyses for all inorganic samples, except two split samples, were conducted by the Arizona Department of Health Services (ADHS) Laboratory in Phoenix, Arizona. The inorganic analyses for the two split samples (UHA-3s and UHA-19s) were conducted by Test America Laboratory in Phoenix, Arizona. A complete listing of inorganic parameters, including laboratory method and Minimum Reporting Level (MRL) for each laboratory is provided in Table 1. Radon samples were submitted to Test America Laboratory and analyzed by Radiation Safety Engineering, Inc. Laboratory in Chandler, Arizona. Isotope samples were analyzed by the Department of Geosciences, Laboratory of Isotope Geochemistry at the University of Arizona in Tucson, Arizona. DATA EVALUATION Quality Assurance Quality-assurance (QA) procedures were followed and quality-control (QC) samples were collected to quantify data bias and variability for the Upper Hassayampa basin study. The design of the QA/QC plan was based on recommendations included in the Quality Assurance Project Plan (QAPP) and the Field Manual For Water Quality Sampling. 1, 5 Types and numbers of QC samples collected for this study include three duplicates, one partial duplicate, two splits, and two equipment blanks for inorganic samples. Based on the QA/QC results, sampling procedures and laboratory equipment did not significantly affect the groundwater quality samples. Blanks – Three equipment blanks for inorganic analyses were collected and delivered to the ADHS laboratory to ensure adequate decontamination of sampling equipment, and that the filter apparatus and/or de-ionized water were not impacting the groundwater quality sampling.5 Equipment blank samples for major ion and nutrient analyses were collected by filling unpreserved and sulfuric acid preserved bottles with de-ionized water. Equipment blank samples for trace element analysis were collected with de-ionized water that had been filtered into nitric acid preserved bottles. Systematic contamination was judged to occur if more than 50 percent of the equipment blank samples contained measurable quantities of a particular groundwater quality constituent. The equipment blanks contained turbidity and specific conductivity (SC-lab) at expected levels due to impurities in the source water used for the samples. Phosphorus was also detected in one sample. For turbidity, the three blanks had a mean level of 0.04 nephelometric turbidity units (ntu) less than 1 percent of the turbidity mean level for the study and were not considered to be significantly affecting the sample results. Testing indicates turbidity is present at 0.01 ntu in the de-ionized water supplied by the ADHS laboratory, and levels increase with time due to storage in ADEQ carboys.17 For SC, two equipment blanks had a mean value of 2.65 micro-siemens per cm (uS/cm) which was less than 1 percent of the SC mean concentration for the study and was not considered to be significantly affecting the sample results. The SC detections may have occurred when water passing through a deionizing exchange unit normally has an SC value of at least 1 uS/cm. Carbon dioxide from the air can also dissolve in de-ionized water with the resulting bicarbonate and hydrogen ions imparting the observed conductivity.17 For total phosphorus, one blank had a concentration of 0.03 mg/L that is less than 1 percent of the total phosphorus mean level for the study. 9 Table 1. Laboratory Water Methods and Minimum Reporting Levels Used in the Study Constituent Instrumentation ADHS / Test America Water Method ADHS / Test America Minimum Reporting Level Physical Parameters and General Mineral Characteristics Alkalinity Electrometric Titration SM 2320B / M 2320 B 2/6 SC (µS/cm) Electrometric EPA 120.1/ M 2510 B -- / 2 Hardness Titrimetric, EDTA Hardness Calculation pH (su) Electrometric TDS Turbidity (NTU) SM 2340 C / SM 2340B 10 / 1 SM 2340 B -- SM 4500 H-B 0.1 Gravimetric SM 2540C 10 Nephelometric EPA 180.1 0.01 / 0.2 Major Ions Calcium ICP-AES EPA 200.7 1/2 Magnesium ICP-AES EPA 200.7 1 / 0.25 Sodium ICP-AES EPA 200.7 1/2 Potassium Flame AA EPA 200.7 0.5 / 2 Bicarbonate Calculation Calculation / M 2320 B 2 Carbonate Calculation Calculation / M 2320 B 2 Chloride Potentiometric Titration SM 4500 CL D / E 300 5/2 Sulfate Colorimetric EPA 375.4 / E 300 1/2 Nutrients Nitrate as N Colorimetric EPA 353.2 0.02 / 0.1 Nitrite as N Colorimetric EPA 353.2 0.02 / 0.1 Ammonia Colorimetric EPA 350.1/ EPA 350.3 0.02 / 0.5 TKN Colorimetric EPA 351.2 / M 4500NH3 0.05 / 1.3 Total Phosphorus Colorimetric EPA 365.4 / M 4500-PB 0.02 / 0.1 All units are mg/L except as noted 17, 20 Source 10 Table 1. Laboratory Water Methods and Minimum Reporting Levels Used in the Study-Continued Constituent Instrumentation ADHS / Test America Water Method ADHS / Test America Minimum Reporting Level Trace Elements Aluminum ICP-AES EPA 200.7 0.5 / 0.2 Antimony Graphite Furnace AA EPA 200.8 0.005 / 0.003 Arsenic Graphite Furnace AA EPA 200.9 / EPA 200.8 0.005 / 0.001 Barium ICP-AES EPA 200.8 / EPA 200.7 0.005 to 0.1 / 0.01 Beryllium Graphite Furnace AA EPA 200.9 / EPA 200.8 0.0005 / 0.001 Boron ICP-AES EPA 200.7 0.1 / 0.2 Cadmium Graphite Furnace AA EPA 200.8 0.0005 / 0.001 Chromium Graphite Furnace AA EPA 200.8 / EPA 200.7 0.01 / 0.01 Copper Graphite Furnace AA EPA 200.8 / EPA 200.7 0.01 / 0.01 Fluoride Ion Selective Electrode SM 4500 F-C 0.1 / 0.4 Iron ICP-AES EPA 200.7 0.1 / 0.05 Lead Graphite Furnace AA EPA 200.8 0.005 / 0.001 Manganese ICP-AES EPA 200.7 0.05 / 0.01 Mercury Cold Vapor AA SM 3112 B / EPA 245.1 0.0002 Nickel ICP-AES EPA 200.7 0.1 / 0.01 Selenium Graphite Furnace AA EPA 200.9 / EPA 200.8 0.005 / 0.002 Silver Graphite Furnace AA EPA 200.9 / EPA 200.7 0.001 / 0.01 Strontium ICP-AES EPA 200.7 0.1 / 0.1 Thallium Graphite Furnace AA EPA 200.9 / EPA 200.8 0.002 / 0.001 Zinc ICP-AES EPA 200.7 0.05 Radionuclides Radon Liquid scintillation counter All units are mg/L Source EPA 913.1 varies 17, 20 11 Duplicate Samples – Duplicate samples are identical sets of samples collected from the same source at the same time and submitted to the same laboratory. Data from duplicate samples provide a measure of variability from the combined effects of field and laboratory procedures.5 Duplicate samples were collected from sampling sites that were believed to have elevated or unique constituent concentrations as judged by SC-field and pH-field values. Cation/Anion Balances – In theory, water samples exhibit electrical neutrality. Therefore, the sum of milliequivalents per liter (meq/L) of cations should equal the sum of meq/L of anions. However, this neutrality rarely occurs due to unavoidable variation inherent in all water quality analyses. Still, if the cation/anion balance is found to be within acceptable limits, it can be assumed there are no gross errors in concentrations reported for major ions.13 Three duplicate samples and one partial duplicate sample were collected and submitted to the ADHS laboratory for this study. Analytical results indicate that of the 40 constituents examined, 20 had concentrations above the MRL. The duplicate samples had an excellent correlation as the maximum variation between constituents was less than 5 percent except for total phosphorus (9 percent), TKN (10 percent), and turbidity (32 percent) (Table 2). Overall, cation/anion meq/L balances of Upper Hassayampa basin samples were significantly correlated (regression analysis, p ≤ 0.01). Of the 34 samples, all were within +/-5 percent. Nineteen samples had low cation/high anion sums; 15 samples had high cation/low anion sums. Split Samples – Split samples are identical sets of samples collected from the same source at the same time that are submitted to two different laboratories to check for laboratory differences.5 Three inorganic split samples were collected and distributed between the ADHS and Test America labs. The analytical results were evaluated by examining the variability in constituent concentrations in terms of absolute levels and as the percent difference. Analytical results indicate that of the 36 constituents examined, 20 had concentrations above MRLs for both ADHS and Test America laboratories (Table 3). The maximum variation between constituents was below 5 percent except for zinc (10 percent), chloride (15 percent), potassium (21 percent), turbidity (28 percent), copper (90 percent), and TKN (95 percent). Split samples were also evaluated using the nonparametric Sign test to determine if there were any significant differences between ADHS laboratory and Test America laboratory analytical results.27 There were no significant differences in constituent concentrations between the labs (Sign test, p ≤ 0.05). Based on the results of blank, duplicate, and split samples collected for this study, no significant QA/QC problems were apparent with the study. Data Validation SC/TDS –- The SC and TDS concentrations measured by contract laboratories were significantly correlated as were SC-field and TDS concentrations (regression analysis, r = 0.98, p ≤ 0.01). The TDS concentration in mg/L should be from 0.55 to 0.75 times the SC in µS/cm for groundwater up to several thousand TDS mg/L.13 Groundwater high in bicarbonate and chloride will have a multiplication factor near the lower end of this range; groundwater high in sulfate may reach or even exceed the higher factor. The relationship of TDS to SC becomes undefined with very high or low concentrations of dissolved solids.13 SC –- The SC measured in the field at the time of sampling was significantly correlated with the SC measured by contract laboratories (regression analysis, r = 0.99, p ≤ 0.01). Hardness – Concentrations of laboratory-measured and calculated values of hardness were significantly correlated (regression analysis, r = 0.99, p ≤ 0.01). Hardness concentrations were calculated using the following formula: [(calcium x 2.497) + (magnesium x 4.118)]. 13 pH – The pH value is closely related to the environment of the water and is likely to be altered by sampling and storage.13 The pH values measured in the field using a YSI meter at the time of sampling were not significantly correlated with laboratory pH values (regression analysis, r = 0.36, p ≥ 0.05). The analytical work for this study was subjected to four QA/QC correlations and considered valid based on the following results. 13 12 Table 2. Summary Results of Duplicate Samples from ADHS Laboratory Parameter Number of Dup. Samples Difference in Percent Minimum Maximum Difference in Concentrations Median Minimum Maximum Median Physical Parameters and General Mineral Characteristics Alk., Total 3 0% 2% 0% 0 10 6 SC (µS/cm) 3 0% 1% 0% 0 10 6 Hardness 3 0% 3% 2% 0 20 10 pH (su) 3 0% 1% 3% 0 0.4 0.1 TDS 3 0% 2% 1% 0 10 10 Turb. (ntu) 3 4% 32 % 7% 0.01 1 0.49 Major Ions Calcium 4 0% 3% 2% 0.3 4 3 Magnesium 4 0% 3% 2% 0 1 1 Sodium 4 0% 1% 0% 0 2 1 Potassium 4 0% 2% 0% 0 0.1 0 Bicarbonate 3 0% 2% 0% 0 10 0 Chloride 3 0% 0% 0% 0 0 0 Sulfate 3 0% 0% 0% 0 0 0 Nutrients Nitrate (as N) 3 0% 5% 2% 0 0.1 0.1 Phosphorus, T. 3 0% 9% 1% 0 0.005 0.001 TKN * 1 - - 10 % - - 0.03 Trace Elements Barium 1 - - 0% - - 0 Boron 2 0% 5% - 0 0.1 - Fluoride 3 0% 2% 0% 0 0.1 0 Zinc** 1 - - 1% - - 0.1 All concentration units are mg/L except as noted with certain physical parameters. * = TKN was detected in one sample (UHA-2) at a concentration of 0.082 mg/L and not detected in the duplicate (UHA-2D) ** = Zinc was detected in one sample (UHA-22) at a concentration of 0.41 mg/L and not detected in the duplicate (UHA-22D) Copper was detected in two samples (UHA-7 and UHA-8) and not detected in the duplicate samples (UHA-7D and UHA-9) Nickel was detected in one sample (UHA-8) at a concentration of 0.12 mg/L and not detected in the duplicate samples (UHA-9) 13 Table 3. Summary Results of Split Samples between ADHS / Test America Labs Constituents Number of Split Sites Difference in Percent Difference in Levels Significance Minimum Maximum Minimum Maximum Physical Parameters and General Mineral Characteristics Alkalinity, total 3 0% 3% 0 12 ns SC (µS/cm) 3 0% 2% 0 20 ns Hardness 2 1% 4% 8 10 ns pH (su) 3 0% 3% 0.1 0.38 ns TDS 3 0% 5% 0 100 ns Turbidity (ntu) 1 28 % 28 % 1.5 1.5 ns Major Ions Calcium 3 2% 5% 2 10 ns Magnesium 3 1% 4% 1 1 ns Sodium 3 0% 3% 0 2 ns Potassium 3 11 % 21 % 1.5 1.9 ns Chloride 3 0% 15 % 0 9 ns Sulfate 3 0% 9% 0 9 ns Nutrients Nitrate as N 1 4% 4% 0.08 0.08 ns TKN* 1 95 % 95 % 16.6 16.6 ns Trace Elements Barium 1 4% 4% 0.008 0.008 ns Chromium 1 0% 0% 0 0 ns Copper 1 90 % 90 % 0.1139 0.1139 ns Fluoride 3 0% 4% 0 0.03 ns Zinc 2 0% 10 % 0 0.03 ns ns = No significant (p  ≤ 0.05) difference All units are mg/L except as noted * = TKN was detected by Test America in (UHA-3S) at 1.1 mg/L and not detected in the ADHS split sample (UHA-3) Ammonia was detected by Test America in (UHA-19S) at 0.68 mg/L and not detected in the ADHS split sample (UHA-19) Total phosphorus was detected by ADHS in (UHA-16) at 0.074 mg/L and not detected in the Test Am. split sample (UHA-17a) Nickel was detected by ADHS in (UHA-16) at 0.25 mg/L and not detected in the Test America split sample (UHA-17a) Zinc was detected by Test America in (UHA-17a) at 0.076 mg/L and not detected in the ADHS split sample (UHA-16) 14 Statistical Considerations Various statistical analyses were used to examine the groundwater quality data of the study. All statistical tests were conducted using SYSTAT software.27 Data Normality: Data associated with 22 constituents were tested for non-transformed normality using the Kolmogorov-Smirnov onesample test with the Lilliefors option.6 Results of this test revealed that 17 of the 22 constituents examined were not normally distributed. Only five constituents were normally distributed: temperature, pH-field, bicarbonate, total alkalinity, and oxygen. Spatial Relationships: The non-parametric KruskalWallis test using untransformed data was applied to investigate the hypothesis that constituent concentrations from groundwater sites having different aquifers were the same. The Kruskal-Wallis test uses the differences, but also incorporates information about the magnitude of each difference.27 The null hypothesis of identical mean values for all data sets within each test was rejected if the probability of obtaining identical means by chance was less than or equal to 0.05. The KruskalWallis test is not valid for data sets with greater than 50 percent of the constituent concentrations below the MRL.12 Correlation Between Constituents: In order to assess the strength of association between constituents, their concentrations were compared to each other using the non-parametric Kendall’s tau-b test. Kendall’s correlation coefficient varies between -1 and +1; with a value of +1 indicating that a variable can be predicted perfectly by a positive linear function of the other, and vice versa. A value of -1 indicates a perfect inverse or negative relationship. The results of the Kendall’s tau-b test were then subjected to a probability test to determine which of the individual pair wise correlations were significant.27 The Kendall’s tau-b test is not valid for data sets with greater than 50 percent of the constituent concentrations below the MRL.12 8.5 Diagram 1 – The 34 samples collected in the Upper Hassayampa basin are plotted according to their pH-field and pH-laboratory values. The graph shows the weak correlation between these two related parameters. The relationship is described by the regression equation: y = 0.32x + 5.3, r = 0.36. The pH value is closely related to the environment of the water and is likely to be altered by sampling and storage.13 pH-lab (su) 8.0 7.5 7.0 6.5 6 7 8 9 pH-field (su) 15 GROUNDWATER SAMPLING RESULTS Water Quality Standards/Guidelines The ADEQ ambient groundwater program characterizes regional groundwater quality. An important determination ADEQ makes concerning the collected samples is how the analytical results compare to various drinking water quality standards. ADEQ used three sets of drinking water standards that reflect the best current scientific and technical judgment available to evaluate the suitability of groundwater in the basin for drinking water use: • • • Federal Safe Drinking Water (SDW) Primary Maximum Contaminant Levels (MCLs). These enforceable health-based standards establish the maximum concentration of a constituent allowed in water supplied by public systems.25 State of Arizona Aquifer Water Quality Standards. These apply to aquifers that are classified for drinking water protected use. All aquifers within Arizona are currently classified and protected for drinking water use. These enforceable State standards are identical to the federal Primary MCLs except for arsenic which is at 0.05 mg/L compared with the federal Primary MCL of 0.01 mg/L. 2 Federal SDW Secondary MCLs. These nonenforceable aesthetics-based guidelines define the maximum concentration of a constituent that can be present without imparting unpleasant taste, color, odor, or other aesthetic effects on the water.25 Health-based drinking water quality standards (such as Primary MCLs) are based on the lifetime consumption (70 years) of two liters of water per day and, as such, are chronic not acute standards.25 Exceedances of specific constituents for each groundwater site is found in Appendix B. Overall Results – Of the 34 sites sampled in the Upper Hassayampa study, 20 sites met all healthbased and aesthetics-based, water quality standards (excluding the proposed radon standard discussed below). Of the 34 sites sampled in the Upper Hassayampa study, health-based water quality standards were exceeded at 9 sites (27 percent). Constituents above Primary MCLs include arsenic (1 site), gross alpha (5 sites), and nitrate (4 sites). Inorganic Constituent Results - Of the 34 sites sampled for the full suite of inorganic constituents (excluding radionuclide sample results) in the Upper Hassayampa study, 20 sites (59 percent) met all health-based and aesthetics-based, water quality standards. Health-based Primary MCL water quality standards and State aquifer water quality standards were exceeded at 5 sites (15 percent) of the 34 sites (Map 3; Table 4). Constituents above Primary MCLs include arsenic (1 site) and nitrate (4 sites). Potential impacts of these Primary MCL exceedances are given in Table 5. Aesthetics-based Secondary MCL water quality guidelines were exceeded at 13 of 34 sites (38 percent; Map 3; Table 5). Constituents above Secondary MCLs include chloride (1 site), fluoride (4 sites), iron (2 sites), manganese (4 sites), sulfate (1 site), TDS (8 sites). Potential impacts of these Secondary MCL exceedances are given in Table 5. Radon Results - Of the 17 sites sampled for radon, none exceeded the proposed 4,000 picocuries per liter (pCi/L) standard that would apply if Arizona establishes an enhanced multimedia program to address the health risks from radon in indoor air. Eight sites exceeded the proposed 300 pCi/L standard (Table 4; Map 4) that would apply if Arizona doesn’t develop a multimedia program. 25 Suitability for Irrigation The groundwater at each sample site was assessed as to its suitability for irrigation use based on salinity and sodium hazards. Excessive levels of sodium are known to cause physical deterioration of the soil and vegetation. Irrigation water may be classified using SC and the Sodium Adsorption Ratio (SAR) in conjunction with one another.26 Groundwater sites in the Upper Hassayampa basin display a narrow range of irrigation water classifications. Samples had a “low” sodium hazard and a “medium” or “high” salinity hazard (Table 6). Analytical Results Analytical inorganic and radiochemistry results of the Upper Hassayampa basin sample sites are summarized (Table 7) using the following indices: MRLs, number of sample sites over the MRL, upper and lower 95 percent confidence intervals (CI95%), median, and mean. Confidence intervals are a statistical tool which indicates that 95 percent of a constituent’s population lies within the stated confidence interval.27 Specific constituent information for each sampled groundwater site is in Appendix B. 16 17 18 Table 4. Sampled Sites Exceeding Health-based Water Quality Standards or Primary MCLs Constituent Primary MCL Number of Sites Exceeding Primary MCL Highest Concentration Potential Health Effects of MCL Exceedances * Nutrients Nitrite (NO2-N) 1.0 0 - - Nitrate (NO3-N) 10.0 4 19 methemoglobinemia Trace Elements Antimony (Sb) 0.006 0 - - Arsenic (As) 0.01 1 0.010 dermal and nervous system toxicity Arsenic (As) 0.05 0 - - Barium (Ba) 2.0 0 - - Beryllium (Be) 0.004 0 - - Cadmium (Cd) 0.005 0 - - Chromium (Cr) 0.1 0 - - Copper (Cu) 1.3 0 - - Fluoride (F) 4.0 0 - - Lead (Pb) 0.015 0 - - Mercury (Hg) 0.002 0 - - Nickel (Ni) 0.1 0 - - Selenium (Se) 0.05 0 - - Thallium (Tl) 0.002 0 - - Radiochemistry Constituents Gross Alpha 15 5 75 cancer Ra-226+Ra-228 5 0 - - Radon ** 300 8 2,641 cancer Radon ** 4,000 0 - - Uranium 30 0 - - All units are mg/L except gross alpha, radium-226+228 and radon (pCi/L), and uranium (ug/L). * Health-based drinking water quality standards are based on a lifetime consumption of two liters of water per day over a 70-year life span.25 ** Proposed EPA Safe Drinking Water Act standards for radon in drinking water. 25 19 Table 5. Sampled Sites Exceeding Aesthetics-Based (Secondary MCL) Water Quality Standards Constituents Secondary MCL Number of Sites Exceeding Secondary MCLs Concentration Range of Exceedances Aesthetic Effects of MCL Exceedances Physical Parameters pH - field < 6.5 0 - - pH - field > 8.5 0 - - General Mineral Characteristics 500 TDS 8 2,300 hardness; deposits; colored water; staining; salty taste Major Ions Chloride (Cl) 250 1 420 salty taste Sulfate (SO4) 250 1 1,100 salty taste tooth discoloration Trace Elements Fluoride (F) 2.0 4 3.5 Iron (Fe) 0.3 2 0.95 Manganese (Mn) 0.05 4 1.5 Silver (Ag) 0.1 0 - - Zinc (Zn) 5.0 0 - - rusty color; sediment; metallic taste; reddish or orange staining black staining; bitter metallic taste All units mg/L except pH is in standard units (su). Source: 25 Table 6. Sodium and Salinity Hazards for Sampled Sites Hazard Total Sites Low Medium High Very High Sodium Hazard Sodium Adsorption Ratio (SAR) Sample Sites 34 0 - 10 10- 18 18 - 26 > 26 34 0 0 0 Salinity Hazard Specific Conductivity (µS/cm) Sample Sites 34 100–250 250 – 750 750-2250 >2250 1 21 10 2 20 Table 7. Summary Statistics for Groundwater Quality Data Constituent Minimum Reporting Limit (MRL)* # of Samples / Samples Over MRL Median Lower 95% Confidence Interval Mean Upper 95% Confidence Interval Physical Parameters Temperature (oC) 0.1 34 / 32 20.2 18.1 20.0 22.0 pH-field (su) 0.01 34 / 33 7.28 7.21 7.35 7.49 pH-lab (su) 0.01 34 / 34 7.66 7.56 7.68 7.81 0.01 / 0.20 34 / 34 1.1 0.5 7.5 14.4 235 264 294 Turbidity (ntu) General Mineral Characteristics T. Alkalinity 2.0 / 6.0 34 / 34 260 Phenol. Alk. 2.0 / 6.0 34 / 0 SC-field (µS/cm) N/A 34 / 34 717 616 784 952 SC-lab (µS/cm) N/A / 2.0 34 / 34 665 593 769 945 Hardness-lab 10 / 6 34 / 34 260 232 306 379 TDS 10 / 20 34 / 34 410 349 482 615 > 50% of data below MRL Major Ions Calcium 5/2 34 / 34 78 65 85 105 1.0 / 0.25 34 / 34 20 18 24 30 5/2 34 / 34 34 31 45 59 Potassium 0.5 / 2.0 34 / 33 2.1 1.9 2.6 3.2 Bicarbonate 2.0 / 6.0 34 / 34 320 285 321 357 Carbonate 2.0 / 6.0 34 / 0 Chloride 1 / 20 34 / 33 26 20 45 70 Sulfate 10 / 20 34 / 33 34 9 73 138 1.3 2.8 4.3 Magnesium Sodium > 50% of data below MRL Nutrients Nitrate (as N) 0.02 / 0.20 34 / 28 1.3 Nitrite (as N) 0.02 / 0.20 34 / 1 > 50% of data below MRL TKN 0.05 / 1.0 34 / 18 > 50% of data below MRL Ammonia 0.02 / 0.05 34 / 1 > 50% of data below MRL T. Phosphorus 0.02 / 0.10 34 / 15 > 50% of data below MRL 21 Table 7. Summary Statistics for Groundwater Quality Data—Continued Constituent Minimum Reporting Limit (MRL)* # of Samples / Samples Over MRL Median Lower 95% Confidence Interval Mean Upper 95% Confidence Interval Trace Elements Aluminum 0.5 / 0.2 22 / 0 > 50% of data below MRL Antimony 0.005 / 0.003 34 / 0 > 50% of data below MRL Arsenic 0.01 / 0.001 34 / 3 > 50% of data below MRL Barium 0.1 / 0.001 34 / 14 > 50% of data below MRL 0.0005 / 0.001 34 / 0 > 50% of data below MRL 0.1 / 0.2 34 / 9 > 50% of data below MRL Cadmium 0.001 34 / 0 > 50% of data below MRL Chromium 0.01 / 0.001 34 / 3 > 50% of data below MRL Copper 0.01 / 0.001 34 / 4 > 50% of data below MRL Fluoride 0.2 / 0.4 34 / 34 Iron 0.1 / 0.05 34 / 4 > 50% of data below MRL Lead 0.005 / 0.001 34 / 0 > 50% of data below MRL 0.05 / 0.01 34 / 4 > 50% of data below MRL 0.0005 / 0.0002 34 / 0 > 50% of data below MRL 0.1 / 0.01 34 / 0 > 50% of data below MRL 0.005 / 0.002 34 / 0 >50% of data below MRL 0.001 34 / 0 > 50% of data below MRL 0.002 / 0.001 34 / 0 > 50% of data below MRL 0.05 34 / 16 > 50% of data below MRL Beryllium Boron Manganese Mercury Nickel Selenium Silver Thallium Zinc 0.5 0.5 0.8 1.1 Radiochemical Radon (pCi/L) Varies 17 / 17 264 184 307 430 Isotopes Oxygen-18 ** Varies 34 / 34 - 9.4 - 9.8 - 9.4 - 9.1 Deuterium ** Varies 34 / 34 - 66.0 - 68.9 - 67.2 - 65.6 * = ADHS MRL / Test America MRL All units mg/L except where noted or ** = 0/00 22 GROUNDWATER COMPOSITION General Summary The water chemistry at the 34 sample sites in the Upper Hassayampa basin (in decreasing frequency) include calcium-bicarbonate (18 sites), mixedbicarbonate (12 sites), and calcium-chloride, calciummixed, mixed-sulfate, and mixed-mixed (1 site apiece) (Diagram 2 – middle figure) (Map 5). Calcium was the dominant cation at 20 sites. At 14 sites the composition was mixed as there was no dominant cation (Diagram 2 – left figure). The dominant anion was bicarbonate at 30 sites and chloride and sulfate at one site apiece. The composition was mixed as there was no dominant anion at two sites (Diagram 2 – right figure). Diagram 2 – Samples collected in the Upper Hassayampa basin is predominantly a calcium-bicarbonate or mixed-bicarbonate chemistry which is reflective of young groundwater that has been recently recharged.18 23 24 At 29 sites, levels of pH field were all slightly alkaline (above 7 su) and 2 sites were above 8 su. At 5 sites, pH-field levels were slightly acidic (below 7 su) 11 TDS concentrations were considered fresh (below 999 mg/L) at 32 sites and slightly saline (1,000 – 3,000 mg/L) at 2 sites (Map 6).11 Hardness concentrations were soft (below 75 mg/L) at 0 sites, moderately hard (75 – 150 mg/L) at 2 sites, hard (150 – 300 mg/L) at 22 sites, very hard (300 600 mg/L) at 6 sites, and extremely hard (above 600 mg/L) at 2 sites (Map 7).8 Nitrate (as nitrogen) concentrations at most sites may have been influenced by human activities (Diagram 3). Nitrate concentrations were divided into natural background (8 sites at < 0.2 mg/L), may or may not indicate human influence (20 sites at 0.2 – 3.0 mg/L), may result from human activities (2 sites at 3.0 – 10 mg/L), and probably result from human activities (4 sites > 10 mg/L).15 Most trace elements such as aluminum, antimony, arsenic, beryllium, boron, cadmium, chromium, copper, iron, lead, manganese, mercury, nickel, selenium, silver, and thallium were rarely – if ever detected. Only barium, fluoride, and zinc were detected at more than 25 percent of the sites. Diagram 3. Nitrate Source of Upper Hassayampa Basin Samples 12% 24% 6% Probably Natural Maybe Natural Maybe Human Probably Human 58% Diagram 3 – In the Upper Hassayampa basin, nitrate (as nitrogen) concentrations vary from non-detect (0.02 mg/L) to 19 mg/L. The Primary MCL for nitrate (as nitrogen) is 10 mg/L. Likely nitrogen sources for the basin’s nitrate concentrations range from “probably natural” to “probably human” based on research published in a U.S. Geological Survey water supply paper. 15 25 26 27 Constituent Co-Variation The correlations between different chemical parameters were analyzed to determine the relationship between the constituents that were sampled. The strength of association between the chemical constituents allows for the identification of broad water quality patterns within a basin. The results of each combination of constituents were examined for statistically-significant positive or negative correlations. A positive correlation occurs when, as the level of a constituent increases or decreases, the concentration of another constituent also correspondingly increases or decreases. A negative correlation occurs when, as the concentration of a constituent increases, the concentration of another constituent decreases, and vice-versa. A positive correlation indicates a direct relationship between constituent concentrations; a negative correlation indicates an inverse relationship.27 Several significant correlations occurred among the 34 sample sites (Table 8, Kendall’s tau-b test, p ≤ 0.05). Four groups of correlations were identified: • The following constituents were all positively correlated with each other: TDS, SC, hardness, calcium, magnesium, sodium, bicarbonate (Diagram 4), chloride, sulfate, fluoride, and radon. • Fluoride had a strong positive correlation with sodium and chloride. • Nitrate was positively correlated oxygen. with TDS concentrations are best predicted among major ions by calcium concentrations (standard coefficient = 0.37), among cations by calcium concentrations (standard coefficient = 0.52) and among anions, by bicarbonate concentrations (standard coefficient = 0.69) (multiple regression analysis, p ≤ 0.01). 600 Diagram 4 – The graph illustrates a positive correlation between two constituents; as hardness concentrations increase, bicarbonate concentrations also increase. This relationship is described by the regression equation: y = 0.30x + 231 (r = 0.60). Both hardness and bicarbonate commonly occur in recharge areas and this relationship has been found in other Arizona groundwater basins. 18 Bicarbonate (mg/L) 500 400 300 200 100 0 500 1000 1500 Hardness (mg/L) 28 Table 8. Correlation Among Groundwater Quality Constituent Concentrations Constituent Temperature pH-field pH-lab SC-field TDS Hardness Calcium Magnesium Sodium Potassium Bicarbonate Chloride Sulfate Temp pH-f pHlab * SC-f ++ TDS ++ + ** Hard Ca Mg Na K Physical Parameters ** ** ++ ++ ++ + ++ ** ** ** ** General Mineral Characteristics ** ** ** ** ** ** ** Major Ions ** * ** ** Bic Cl SO4 NO3 F ** * + * ** ++ Radon D * * * * ++ ** + ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** * ** ** ** ** * ** * ** O * ** ** ** ** * Nutrients Nitrate * Trace Elements Fluoride * Radioactivity Radon Isotopes Oxygen Deuterium ** Blank cell = not a significant relationship between constituent concentrations * = Significant positive relationship at p ≤ 0.05 ** = Significant positive relationship at p ≤ 0.01 + = Significant negative relationship at p ≤ 0.05 ++ = Significant negative relationship at p ≤ 0.01 29 Oxygen and Hydrogen Isotopes The data for the Upper Hassayampa basin roughly conforms to what would be expected in an arid environment, having a slope of 5.0, with the Local Meteoric Water Line (LMWL) described by the linear equation: δ D = 5.0δ 18O – 27.7 (Diagram 5). The LMWL for the Upper Hassayampa basin (5.0) is higher than a few other basins in Arizona such as Aravaipa Canyon (4.1) and Dripping Springs Wash (4.4). The basin is however, is lower than most other basins in Arizona including Detrital Valley (5.2), Agua Fria (5.3), Bill Williams (5.3), Sacramento Valley (5.5), Big Sandy (6.1), Butler Valley (6.4), Pinal Active Management Area (6.4), Gila Valley (6.4), San Simon (6.5), San Bernardino Valley (6.8), McMullen Valley (7.4), Lake Mohave (7.8), and Ranegras Plain (8.3). 23 Isotope samples generally have values that reflect the elevation at which the sites were located. The five sample sites that are lowest along the LMWL have the lightest signatures from undergoing the least evaporation prior to sampling. These were collected at high elevations in the Bradshaw Mountains. Above these depleted samples are more enriched samples and appear to consist of recharge from lowerelevation precipitation that has undergone more evaporation prior to sampling. The most enriched samples on the graph were from shallow wells along the Hassayampa River. (Map 8). Oxygen and Hydrogen Isotopes Groundwater characterizations using oxygen and hydrogen isotope data may be made with respect to the climate and/or elevation where the water originated, residence within the aquifer, and whether or not the water was exposed to extensive evaporation prior to collection.7 This is accomplished by comparing oxygen-18 isotopes (δ 18O) and deuterium (δ D), an isotope of hydrogen, data to the Global Meteoric Water Line (GMWL). The GMWL is described by the linear equation: δ D = 8 δ 18O + 10 where δ D is deuterium in parts per thousand (per mil, 0/00), 8 is the slope of the line, δ 18O is oxygen-18 0 /00, and 10 is the y-intercept.9 The GMWL is the standard by which water samples are compared and is a universal reference standard based on worldwide precipitation without the effects of evaporation. Isotopic data from a region may be plotted to create a Local Meteoric Water Line (LMWL) which is affected by varying climatic and geographic factors. When the LMWL is compared to the GMWL, inferences may be made about the origin or history of the local water.9 The LMWL created by δ 18O and δ D values for samples collected at sites in the Upper Hassayampa basin plot mostly to the right of the GMWL. Meteoric waters exposed to evaporation are enriched and characteristically plot increasingly below and to the right of the GMWL. Evaporation tends to preferentially contain a higher percentage of lighter isotopes in the vapor phase and causes the water that remains behind to be isotopically heavier. In contrast, meteoric waters that experience little evaporation are depleted and tend to plot increasing to the left of the GMWL and are isotopically lighter. 7 Groundwater from arid environments is typically subject to evaporation, which enriches δ D and δ 18O, resulting in a lower slope value (usually between 3 and 6) as compared to the slope of 8 associated with the GMWL.7 Diagram 5 – The 34 isotope samples are plotted according to their oxygen-18 and deuterium values and form the Local Meteoric Water Line. 30 31 Groundwater Quality Variation Between Two Recharge Groups – Twenty (20) groundwater quality constituents were compared between two recharge groups: enriched samples collected at lower elevations (15 sites) and depleted samples collected at higher elevations (5 sites). Significant concentration differences were found with eight constituents: temperature, pH-lab, sodium (Diagram 6), potassium, chloride, fluoride (Diagram 7 and Map 9), oxygen-18 and deuterium (KruskalWallis test, p ≤ 0.05). In all these instances, sites with enriched samples had significantly higher constituent concentrations than sites with depleted samples. Complete statistical results are in Table 9 and 95 percent confidence intervals for significantly different groups based on isotope recharge sources are in Table 10. 250 Diagram 6 – Sites consisting of enriched samples have significantly higher sodium concentrations than sites consisting of depleted samples (KruskalWallis, p ≤ 0.05). The depleted samples, collected at high elevations in the Bradshaw Mountains, have undergone the least evaporation prior to sampling. Recharge areas typically have low sodium concentrations though sodium often becomes the dominant cation in downgradient areas as a result of silicate weathering, halite dissolution, and ion exchange. 18 150 100 50 0 Depleted Enriched Recharge Group 4 Diagram 7 – Sites consisting of enriched samples have significantly higher fluoride concentrations than sites consisting of depleted samples (KruskalWallis, p ≤ 0.05). Hydroxyl ion exchange provides control on fluoride concentrations below 5 mg/L. As groundwater pH values increase downgradient, greater levels of hydroxyl ions may affect an exchange of hydroxyl for fluoride ions thereby increasing the concentrations of fluoride in solution. 18 3 Fluoride (mg/L) Sodium (mg/L) 200 2 1 0 Depleted Enriched Recharge Group 32 33 Table 9. Variation in Groundwater Quality Constituent Concentrations between Two Recharge Groups Constituent Significance Significant Differences Between Recharge Groups Temperature - field * Enriched > Depleted pH – field ns - pH – lab * Enriched > Depleted SC - field ns - SC - lab ns - TDS ns - Turbidity ns - Hardness ns - Calcium ns - Magnesium ns - Sodium ** Enriched > Depleted Potassium * Enriched > Depleted Bicarbonate ns - Chloride ** Enriched > Depleted Sulfate ns - Nitrate (as N) ns - Fluoride * Enriched > Depleted Radon ns - Oxygen ** Enriched > Depleted Deuterium ** Enriched > Depleted ns = not significant * = significant at p ≤ 0.05 or 95% confidence level ** = significant at p ≤ 0.01 or 99% confidence level 34 Table 10. Summary Statistics for Two Recharge Groups with Significant Constituent Differences Constituent Significance Depleted Enriched Temperature – field (oC) * 8.7 to 22.4 18.8 to 22.9 pH – field (su) ns - - pH – lab (su) * 6.94 to 7.87 7.61 to 7.86 SC - field (µS/cm) ns - - SC - lab (µS/cm) ns - - TDS ns - - Turbidity ns - - Hardness ns - - Calcium ns - - Magnesium ns - - Sodium ** 5 to 25 35 to 66 Potassium * -0.9 to 4.4 2.0 to 3.4 Bicarbonate ns - - Chloride ** -2 to 26 21 to 80 Sulfate ns - - Nitrate (as N) ns - - Fluoride * 0.0 to 0.6 0.6 to 1.2 Radon ns - - Oxygen (0/00) ** -11.4 to -10.7 -9.40 to -8.91 Deuterium (0/00) ** -77.8 to -75.8 -66.7 to -64.5 ns = not significant * = significant at p ≤ 0.05 or 95% confidence level ** = significant at p ≤ 0.01 or 99% confidence level All units are mg/L except where indicated. 35 Between Two Geologic Groups - Twenty groundwater quality constituents were compared between two broad geologic types: consolidated crystalline rock (16 sites) and unconsolidated sediments (18 sites).4, 16, 19 narrowly missed being significant. All constituents except for turbidity had significantly higher concentrations in samples collected from unconsolidated sediment than from consolidated rock. Significant concentration differences were found with seven constituents: temperature, turbidity, sodium, sulfate, nitrate (Diagram 8 and Map 10), fluoride, and deuterium (Kruskal-Wallis test, p ≤ 0.05). In addition, pH-field (Diagram 9) and oxygen-18 both Complete statistical results are in Table 11 and 95 percent confidence intervals for significantly different groups based on recharge groups are in Table 12. Nitrate as Nitrogen (mg/L) 20 Diagram 8 – Samples collected from sites in unconsolidated sediments have significantly higher nitrate concentrations than sample sites collected from consolidated rock (KruskalWallis, p ≤ 0.05). This pattern may be due to increased residential and commercial development that has occurred in basin-fill areas. 15 10 5 0 Consolidated Unconsolidated Geology pH-field (su) 9 Diagram 9 – Samples collected from sites in unconsolidated sediments have significantly higher pH-field values than samples collected from consolidated rock (Kruskal-Wallis, p ≤ 0.05). In areas of consolidated rock, acidic precipitation averaging 5.8 su percolates into faults and crevices. The recharged groundwater gradually increases in pH downgradient through silicate hydrolysis reactions. 18 8 7 6 Consolidated Unconsolidated Geology 36 37 Table 11. Variation in Groundwater Quality Constituent Concentrations between Two Geologic Groups Constituent Significance Significant Differences Between Geologic Types ** Unconsolidated Sediment > Consolidated Rock pH – field almost Unconsolidated Sediment > Consolidated Rock pH – lab ns - SC - field ns - SC - lab ns - TDS ns - Turbidity * Consolidated Rock > Unconsolidated Sediment Hardness ns - Calcium ns - Magnesium ns - Sodium ** Unconsolidated Sediment > Consolidated Rock Potassium ns - Bicarbonate ns - Chloride ns - Sulfate * Unconsolidated Sediment > Consolidated Rock Nitrate (as N) ** Unconsolidated Sediment > Consolidated Rock Fluoride ** Unconsolidated Sediment > Consolidated Rock Radon ns - Oxygen almost Unconsolidated Sediment > Consolidated Rock * Unconsolidated Sediment > Consolidated Rock Temperature - field Deuterium ns = not significant * = significant at p ≤ 0.05 or 95% confidence level ** = significant at p ≤ 0.01 or 99% confidence level 38 Table 12. Summary Statistics for Two Geologic Groups with Significant Constituent Differences Constituent Significance Consolidated Rock Unconsolidated Sediments Temperature – field (oC) ** 14.7 to 20.4 19.7 to 24.7 pH – field (su) ns 7.00 to 7.41 7.28 to 7.66 pH – lab (su) ns - - SC – field (µS/cm) ns - - SC – lab (µS/cm) ns - - TDS ns - - Turbidity * 1.9 to 13.4 -5.5 to 20.2 Hardness ns - - Calcium ns - - Magnesium ns - - Sodium ** 12 to 63 36 to 67 Potassium ns - - Bicarbonate ns - - Chloride ns - - Sulfate * -51 to 237 38 to 73 Nitrate (as N) ** 0.3 to 1.6 1.7 to 7.0 Fluoride ** 0.2 to 0.8 0.6 to 1.5 Radon ns - - Oxygen (0/00) ns -10.4 to -9.2 -9.4 to -8.9 Deuterium (0/00) * -72.6 to -66.5 -66.5 to 64.0 ns = not significant * = significant at p ≤ 0.05 or 95% confidence level ** = significant at p ≤ 0.01 or 99% confidence level All units mg/L except where indicated. 39 DISCUSSION Groundwater in the Upper Hassayampa basin is generally suitable for drinking water uses based on the water quality results from sampling conducted for this study. Samples from 20 of the 34 sites met all water quality standards. 25 Moreover, samples from four other sites had only minor exceedances of aesthetics-based standards for TDS, iron, and/or manganese, making 24 of the 34 sample sites (71 percent) generally acceptable as a drinking water source. • Of the remaining 10 sample sites, the constituents that most commonly impacted the acceptability of water for drinking purposes were gross alpha and nitrate. These are two of the four constituents that most commonly exceed health-based water quality standards in Arizona. 22 Gross alpha exceeded health-based, water quality standards in radionuclide samples collected from five sites. Radionuclide samples were collected however, at only 12 of the 34 sites, so gross alpha had a 42 percent water quality exceedance rate. This finding is not unexpected as much of the basin consists of granitic geology which is associated with elevated radionuclide concentrations in groundwater.14 Furthermore, some sites such as Coyt Well (UHA-6) also had inactive mines nearby which are strongly connected with elevated radionuclide concentrations.14 Uranium concentrations did not exceed water quality standards but these were tested for in only 3 of the 12 radionuclide samples. All gross alpha exceedances occurred in wells or springs that are used for livestock watering. Future groundwater quality studies in the basin should better characterize gross alpha concentrations by collecting additional radionuclide samples. Nitrate exceeded health-based, water quality standards in samples collected from four wells. Three of the exceedances were just over the 10.0 mg/L nitrate (as nitrogen) standard (11, 11 and 12 mg/L) while a sample from the remaining well was almost double the standard at 19 mg/L. Potential sources of nitrate vary by site. • • The sample (UHA-11) collected at the Parker Dairy Farm Well is likely due to livestock waste from the agricultural operation. Although the well serving the dairy is 1,050 feet deep, the groundwater depth and screened interval are unknown. The sample (UHA-21) collected at the remote Cooper Ranch could be due to • discharges from septic systems as the shallow well was reportedly only 40 feet deep with a water level of 14 feet bls. The sample (UHA-19) collected from the Arrowhead Bar in Congress could also be from septic system discharge, particularly with the greater waste stream created from a commercial business as well as other nearby residences on septic systems in the historic mining town. This conclusion is supported by the sample having a TDS concentration of 1,350 mg/L and a chloride concentration of 420 mg/L, both of which are also indicators of septic system discharge.28 Both of these concentrations exceeded their respective aesthetics-based water quality standards. Furthermore, the TDS concentration is the second highest in the basin and is much greater than the median TDS concentration of 410 mg/L. The chloride concentration is the highest in the basin and greatly exceeds the median chloride concentration of 26 mg/L. The well serving the Arrowhead Bar is 700 feet deep, has a screened interval from 520 to 700 feet, and has an unknown groundwater depth. The sample (UHA-5) collected from Sky Camp Well had the highest nitrate (as nitrogen) concentration in the basin at 19 mg/L. The former windmill that is now powered by a generator and submersible pump is located about four miles northwest of Wickenburg along Constellation Road. The depth of well is not known; perhaps waste from livestock watering at the well contributed to the high nitrate concentration. The only other site which had an exceedance of a health-based water quality standard was a sample (UHA-1) collected from the Flying E Ranch. The 440-feet-deep well had the highest arsenic and fluoride concentrations in the basin; the concentrations of these two constituents are frequently significantly correlated in other Arizona groundwater basins.21 The sample’s arsenic concentration of 0.01 mg/L equaled the health-based water quality standard. The sample’s fluoride concentration of 3.5 mg/L did not exceed the 4.0 health-based standard but exceeded the 2.0 mg/L aesthetics-based standard. The sample also had the highest pH-field value of 8.41 su, just below the aesthetics-based standard and some of softest water (100 mg/L) recorded in the study. The sample chemically appears more similar to groundwater samples collected in the Forepaugh aquifer located in the bordering McMullen Valley basin. 21 40 Fluoride concentrations in groundwater are often controlled by calcium through precipitation or dissolution of the mineral, fluorite. In a chemically closed hydrologic system, calcium is removed from solution by precipitation of calcium carbonate and the formation of smectite clays. Concentrations exceeding 5 mg/L of dissolved fluoride may occur in groundwater depleted in calcium if a source of fluoride ions is available for dissolution.18 The site however, is only partially depleted in calcium and appears to be controlled by processes other than fluorite dissolution. Hydroxyl ion exchange or sorption-desorption reactions have also been cited as providing controls on lower (< 5 mg/L) levels of fluoride. As pH values increase downgradient, greater levels of hydroxyl ions may affect an exchange of hydroxyl for fluoride ions thereby increasing fluoride in solution. 18 The pH levels of the sample (UHA-1) appear to follow this pattern with a pH-field value of 8.41 su. In common with fluoride, arsenic concentrations are effected by reactions with hydroxyl ions. Elevated arsenic concentrations are also influenced by factors such as aquifer residence time, an oxidizing environment, and lithology. 18 Another sample (UHA-6) with unusual water chemistry was collected from Coyt Well located in a remote area about six miles east of Wickenburg. The sample exceeded health-based water quality standards for gross alpha and aesthetics-based water quality standards for TDS, sulfate, fluoride, and manganese. The sample collected from the site had the highest concentrations of TDS (2,300 mg/L) and sulfate (1,100 mg/L) found in the basin. Based on these results, the water quality exceedances appear to be influenced by the nearby historic mining activity. 18 Especially notable is the sulfate result which is almost nine times the next highest concentration found in the basin. The presence of relatively high concentrations of iron, manganese, and TKN combined with a non-detection of nitrate suggest unusual reducing conditions in groundwater produced by the well. 18 The groundwater results from this well appear to be site specific and probably are not reflective of regional groundwater conditions. In the basin, there is some tendency for constituent concentrations to be significantly higher in groundwater sites collected in unconsolidated sediment and/or which consist of enriched recharge. These trends however, do not impact the acceptability of these sites for use as a drinking water source. REFERENCES 1 Arizona Department of Environmental Quality, 1991, Quality Assurance Project Plan: Arizona Department of Environmental Quality Standards Unit, 209 p. 2 Arizona Department of Environmental Quality, 20112012, Arizona Laws Relating to Environmental Quality: St. Paul, Minnesota, West Group Publishing, §49-221-224, p 134-137. 3 Arizona State Land Department, 1997, “Land Ownership - Arizona” GIS coverage: Arizona Land Resource Information Systems, downloaded, 4/7/07. 4 Arizona Department of Water Resources website, 2013, www.azwater.gov/azdwr/default.aspx, accessed 06/14/13. 5 Arizona Water Resources Research Center, 1995, Field Manual for Water-Quality Sampling: Tucson, University of Arizona College of Agriculture, 51 p. 6 Brown, S.L., Yu, W.K., and Munson, B.E., 1996, The impact of agricultural runoff on the pesticide contamination of a river system - A case study on the middle Gila River: Arizona Department of Environmental Quality Open File Report 96-1: Phoenix, Arizona, 50 p. 7 Craig, H., 1961, Isotopic variations in meteoric waters. Science, 133, pp. 1702-1703. 8 Crockett, J.K., 1995. Idaho statewide groundwater quality monitoring program–Summary of results, 1991 through 1993: Idaho Department of Water Resources, Water Information Bulletin No. 50, Part 2, p. 60. 9 Earman, Sam, et al, 2003, An investigation of the properties of the San Bernardino groundwater basin, Arizona and Sonora, Mexico: Hydrology program, New Mexico Institute of Mining and Technology, 283 p. 10 Graf, Charles, 1990, An overview of groundwater contamination in Arizona: Problems and principals: Arizona Department of Environmental Quality seminar, 21 p. 11 Heath, R.C., 1989, Basic ground-water hydrology: U.S. Geological Survey Water-Supply Paper 2220, 84 p. 12 Helsel, D.R. and Hirsch, R.M., 1992, Statistical methods in water resources: New York, Elsevier, 529 p. 13 Hem, J.D., 1985, Study and interpretation of the chemical characteristics of natural water [Third edition]: U.S. Geological Survey Water-Supply Paper 2254, 264 p. 14 Lowry, J.D. and Lowry, S.B., 1988, “Radionuclides in Drinking Waters,” in American Water Works Association Journal, 80 (July), pp. 50-64. 41 28 15 16 Madison, R.J., and Brunett, J.O., 1984, Overview of the occurrence of nitrate in ground water of the United States, in National Water Summary 1984-Water Quality Issues: U.S. Geological Survey Water Supply Paper 2275, pp. 93-105. Bedient, P.B. Rifai, H.S. and Newell, C.J., 1994, Ground Water Contamination: Transport and Remediation: Englewood Cliffs, N.J., Prentice-Hall, Inc. Richard, S.M., Reynolds, S.J., Spencer, J.E. and Pearthree, Pa, P.A., 2000, Geologic map of Arizona: Arizona Geological Survey Map 35, scale 1:1,000,000. 17 Roberts, Isaac, 2008, Personal communication from ADHS staff. 18 Robertson, F.N., 1991, Geochemistry of ground water in alluvial basins of Arizona and adjacent parts of Nevada, New Mexico, and California: U.S. Geological Survey Professional Paper 1406-C, 90 p. 19 Sanger, H.W. and Appel, Cynthia L., 1980, Maps showing ground-water conditions in the Hassayampa area, Maricopa and Yavapai counties, Arizona—1978: U.S. Geological Survey Water Resources Investigations 80-584, 2 sheets, scale, 1:250,000. 20 Test America, 2013, Personal communication from Test America staff. 21 Towne, D.C., 2011, Ambient groundwater quality of the McMullen Valley basin: a 2008-2009 baseline study: Arizona Department of Environmental Quality Open File Report 11-02, 94 p. 22 Towne, Douglas and Jones, Jason, 2011, Groundwater quality in Arizona: a 15 year overview of the ADEQ ambient groundwater monitoring program (19952009): Arizona Department of Environmental Quality Open File Report 11-04, 44 p. 23 Towne, D.C., 2011, Ambient groundwater quality of the Bill Williams basin: a 2003-2009 baseline study: Arizona Department of Environmental Quality Open File Report 11-06, 73 p. 24 University of Arizona Environmental Isotope Laboratory, 2013, Personal communication with Christopher Eastoe. 25 U.S. Environmental Protection Agency website, www.epa.gov/waterscience/criteria/humanhealth/, accessed 3/05/10. 26 U.S. Salinity Laboratory, 1954, Diagnosis and improvement of saline and alkali soils: U.S. Department of Agriculture, Agricultural Research Service, Agriculture Handbook No. 60, 160 p. 27 Wilkinson, L., and Hill, M.A., 1996. Using Systat 6.0 for Windows, Systat: Evanston, Illinois, p. 71-275. 42 Appendix A. Data for Sample Sites, Upper Hassayampa Basin, 2003-2009 Site # Cadastral / Pump Type Latitude Longitude ADWR # ADEQ # Site Name Samples Collected Well Depth Water Depth Perforation Interval 1st Field Trip, February 11, 2003 – Boettcher & Lucci UHA-1 B(7-5)17cca submersible 33°56'48.139" 112°47’39.010" 630737 19004 Flying E Ranch HQ Inorganic, Radon O & H Isotopes 440’ 374’ - UHA-2/2D duplicate B(8-5)23dbb submersible 34°01'12.432" 112°44’38.130" 561978 60581 East of HouseWell Inorganic, Radon O & H Isotopes 200’ 70’ 140-200’ UHA-3/3S split B(8-6)24dad 34°01'10.722" 112°49’18.238" 571452 19334 Moreton Well Inorganic, Radon O & H Isotopes 415’ 338’ 315-415’ UHA-4 B(7-4)17aba submersible 33°57'17.312" 112°41’21.549" 548766 60582 Glinski Well Inorganic, Radiochem O & H Isotopes 355’ 225’ 250-350’ 2nd Field Trip, April 10, 2003 - Boettcher & Lucci UHA-5 B(8-4)27bbd submersible 34°00'40.631" 112°39’45.065" 634092 19325 Sky Camp Well Inorganic, Radiochem O & H Isotopes - - - UHA-6 B(8-3)30dda submersible 34°00'08.472" 112°36’11.544" 801554 60670 Coyt Well Inorganic, Radiochem O & H Isotopes - - - UHA-7/7D duplicate B(10-7)23aaa windmill 34°12'02.745" 112°12’02.270" 614626 19672 Yellow Well Inorganic O & H Isotopes - - - 3rd Field Trip, March 22-23, 2003 – Towne & Boettcher UHA-8/9 partial duplicate B(9-4)16cad submersible 34°07'05.382" 112°40’58.080" 609871 62635 Moralez Well Inorganic, Radiochem Radon, Isotopes 17’ 10’ - UHA-10 B(9-4)10ddd spring 34°07'45.267" 112°39’24.343" - 61081 Sinoski Spring Inorganic, Radiochem Isotopes - - - UHA-11 B(10-5)28bad submersible 34°10'35.049" 112°46’56.582" 520743 61091 Parker Dairy Farm Inorganic, Radiochem Isotopes 1050’ - - UHA-12 B(12.5-2)35cbd submersible 34°25'22.425" 112°26’44.400" 545809 61095 Rebb Well Inorganic, Radiochem Isotopes 160’ 20’ 60-160’ UHA-13 B(12.5-2)35bdc submersible 34°25'34.508" 112°26’31.090" 642867 61096 Norris Well Inorganic, Radiochem Isotopes 450’ 40’ - UHA-14 Hassayampa River At Greg’s - - - - Isotope - - - UHA-15 B(11-3)5bba submersible 34°19'54.054" 112°35’31.271" 649183 61097 Curie Well Inorganic Isotopes 100’ 15’ - UHA-16/17a split B(7-4)20caa submersible 33°55'59.930" 112°41’38.520" 535404 55072 Hassya.Rvr Preserve W Inorganic Isotopes 200’ 19’ 120-200’ UHA-16a Hassayampa River at Preserve - - - - Isotope - - - 4th Field Trip, June 9-11, 2003 – Boettcher & Lucci UHA-17b B(9-3)21cdb spring UHA-18 B(10-6)19bda windmill UHA-19/19S split B(10-6)25bdb submersible UHA-20 34°06'08.7" 112°44’08.6" - 19495 House Spring Inorganic, Radon O & H Isotopes - - - 614622 19659 Buck’s Windmill Inorganic, Radiochem Isotopes - 100’ - 34°10'39.433" 112°49’44.716" 586443 62690 Arrowhead Bar Well Inorganic, Radon O & H Isotopes 700’ 300’ 520-700’ B(9-5)1bbd submersible 34°08'59.189" 112°44’05.223" 643463 19501 Grantham Well Inorganic, Radon O & H Isotopes 180’ 155’ - UHA-21 B(10-3)14ada submersible 34°12'43.714" 112°32’09.492" 624338 19640 Cooper RanchWell Inorganic, Radon O & H Isotopes 40’ 14’ - UHA-22/22D duplicate B(12-4)36aac windmill 34°20'40.116" 112°37’17.301" 614675 67661 Walker Place Mill Inorganic, Radon O & H Isotopes 222’ 150’ - UHA-23 B(13-2)35bc submersible 632365 62618 YMCA Camp Well Inorganic Isotopes - - - UHA-25 B(12.5-1)30bdb spring - 62607 Boundary Spring Inorganic, Radon O & H Isotopes - - - 43 Appendix A. Data for Sample Sites, Upper Hassayampa Basin, 2003-2009---Continued Site # Cadastral / Pump Type Latitude Longitude ADWR # ADEQ # Site Name Samples Collected Well Depth Water Depth Perforation Interval 5th Field Trip, February 22, 2007 – Towne & Smart (Travel Blank AGF-58) UHA-26 B(10-1)16bba spring 34°12'49.383" 112°22’06.701" - 67580 Senator Spring Inorganic, Radiochem Radon, Isotopes - - - UHA-27 B(10-1)8bad spring 34°13'40.294" 112°23’20.570" - 67581 Patterson Spring Inorganic Isotopes - - - UHA-28 B(9-2)3dcb windmill 34°08'48.273" 112°27’16.125" 633348 67582 Up Oak Ck Windmill Inorganic, Radiochem Radon, Isotopes 65’ 12’ - UHA-29 B(9-2)4acc windmill 34°09'05.415" 112°28’20.136" 633349 62606 ML Windmill Inorganic, Radiochem Radon, Isotopes 60’ 20’ - 6th Field Trip, March 7, 2007 – Towne & Boettcher UHA-30 Hassayampa River at Wagoner Rd - - - - Isotope - - - UHA-31 B(12-3)33c spring 34°20'15.473" 112°34’37.056" - 67662 Collins Spring Inorganic Isotopes - - - 35’ 22’ 15-35’ 7th Field Trip, September 18, 2008 – Towne & Mitchell (Equipment Blank - MMU-121) UHA-32 B(7-5)1ddc bailer 33°58'17.305" 112°43'24.076" 588564 71762 MW-5 Inorganic, Radiochem Isotopes 8th Field Trip, January 21, 2009 – Towne (Travel Blank, BWM- 85) UHA-33 B(10-2)30bbc spring 34°10'59.775" 112°31'00.725" - 72861 Campbell Flat Spring Inorganic, Isotopes - - - UHA-34 Minnehaha Creek at Wagoner Road - - - - Isotope - - - UHA-35 B(10-3)11acd submersible 34°13'33.418" 112°32'25.470" 628604 19636 Diamond Two House Inorganic, Radon Isotopes 328’ 10’ - UHA-36 B(10-3)2cdd submersible 34°13'59.450" 112°32'41.269" 901948 72862 Z Triangle House Wl Inorganic, Isotopes 142’ 21’ 102-142’ UHA-37 B(11-3)15bba submersible 34°18'10.730" 112°33'51.911" 506299 19724 TK Bar Ranch Wl Inorganic, Radon Isotopes 300’ 60’ - UHA-38 B(11-3)10ccb submersible 34°18'23.676" 112°33'55.279" 622261 72863 TK Bar Rn Artesian Inorganic, Radon Isotopes 575’ 100’ - UHA-39 B(12-3)30bdd windmill 34°21'17.595" 112°36'39.893" 601427 72864 Hackberry Windmill Inorganic, Isotopes 252’ 230’ - 44 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009---Continued Site # MCL Exceedances Temp (oC) pH-field (su) pH-lab (su) SC-field (µS/cm) SC-lab (µS/cm) TDS (mg/L) Hard (mg/L) Hard - cal (mg/L) Turb (ntu) UHA-1 As, F 24.5 8.41 8.0 321 350 220 100 100 0.06 UHA-2/2D - 20.1 7.87 7.75 493 540 315 200 205 0.075 UHA-3/3S - 26.5 8.11 7.9 332 360 200 96 93 0.26 UHA-4 - 26.3 7.61 7.5 443 480 300 190 200 0.04 NO3 24.0 7.69 7.5 772 800 450 290 280 3.2 21.9 6.92 7.2 2738 2900 2300 1300 1100 32 23.2 7.60 7.5 908 935 580 265 260 11.5 UHA-5 UHA-7/7D TDS, SO4 F, Mn, Gross α TDS, F, Gross α UHA-8/9 TDS 20.1 7.02 7.4 874 870 530 260 250 0.27 UHA-10 - - - 7.6 744 700 410 260 250 0.62 UHA-11 TDS, NO3 Gross α 29.4 7.26 7.4 1189 1200 710 390 390 0.22 UHA-12 - 12.7 6.45 7.0 522 520 290 260 270 5.4 UHA-13 - 12.6 6.83 7.4 481 460 260 220 230 7.9 UHA-15 - 18.3 6.91 7.5 589 590 330 260 280 ND UHA-16 - 24.2 7.34 7.715 692 670 410 240 260 ND UHA-17 - 23.3 7.66 8.0 641 650 390 260 270 35 UHA-18 F, Fe, Gross α 25.7 7.48 7.0 718 710 440 260 270 0.96 UHA-19/19S TDS, Cl, NO3 Radon 26.6 6.99 7.39 2191 2200 1350 755 800 2.65 UHA-20 - 24.8 7.19 7.4 826 830 490 330 340 ND UHA-21 TDS, NO3 Radon 19.3 7.15 7.5 1168 1100 700 460 480 0.34 UHA-22/22D - 18.5 7.36 7.4 643 647 395 320 320 0.75 UHA-23 - 15.8 7.84 7.4 470 490 280 200 220 4.2 UHA-25 Radon 25.0 7.18 7.2 764 770 440 340 360 0.48 UHA-26 Mn, Radon 11.7 7.12 8.0 718 630 360 270 310 14 UHA-27 Fe, Mn 8.1 7.18 8.0 468 340 240 170 170 6.8 UHA-28 Radon 17.9 7.03 8.0 804 720 420 280 280 1.8 UHA-29 TDS, Gross α Radon 17.3 7.04 8.1 1003 920 560 340 330 4.4 UHA-31 Mn 15.2 7.28 8.0 946 780 470 390 360 7.3 UHA-32 - 21.2 7.28 8.0 715 660 420 260 250 110 UHA-6 italics = constituent exceeded holding time 45 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009---Continued Site # Calcium (mg/L) Magnesium (mg/L) Sodium (mg/L) Potassium (mg/L) T. Alk (mg/L) Bicarbonate (mg/L) Carbonate (mg/L) Chloride (mg/L) Sulfate (mg/L) UHA-1 25 9.5 31 3.1 130 160 ND 13 11 UHA-2/2D 55 16.5 31 2.45 200 240 ND 23 38 UHA-3/3S 20 11.5 37 3.65 140 170 ND 17.5 14 UHA-4 56 14 21 3.4 210 260 ND 9.6 14 UHA-5 75 28 36 2.8 190 230 ND 66 26 UHA-6 340 100 200 6.6 430 520 ND 150 1100 UHA-7/7D 80.5 15 92.5 1.9 265 325 ND 79 86 UHA-8/9 73 21.5 83 1.5 340 410 ND 37 43 UHA-10 80 16 40 2.0 280 340 ND 40 23 UHA-11 120 22 84 3.3 280 340 ND 90 130 UHA-12 86 14 5.2 0.61 243 269 ND 3.9 27 UHA-13 65 17 11 ND 216 264 ND 6.7 16 UHA-15 76 21 16 1.6 260 320 ND 17 8.9 UHA-16 67 20.5 44 2.65 234 278 ND 31.5 51.5 UHA-17 88 12 35 3.4 280 340 ND 38 11 UHA-18 83 15 45 0.82 210 260 ND 53 60 UHA-19/19S 235 48.5 140 8.75 295 350 ND 420 130 UHA-20 82 34 48 1.6 318 388 ND 46 67 UHA-21 98 56 77 6.6 440 540 ND 51 86 UHA-22/22D 91.85 22.95 13 1.3 280 340 ND 30 11 UHA-23 57 19 13 1.1 190 230 ND 23 18 UHA-25 86 34 26 5.5 300 370 ND 25 66 UHA-26 97 17 19 1.2 270 320 ND ND 100 UHA-27 44 15 17 2.1 170 210 ND 11 33 UHA-28 79 21 58 3.0 360 440 ND 32 30 UHA-29 76 33 84 3.1 470 570 ND 53 21 UHA-31 100 26 28 0.81 410 500 ND 26 ND UHA-32 69 20 42 2.2 260 320 ND 28 52 46 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009--Continued Site # Nitrate-N (mg/L) Nitrite-N (mg/L) TKN (mg/L) Ammonia (mg/L) T. Phosphorus (mg/L) SAR (value) Irrigation Quality Cyanide (ug/L) Aluminum (mg/L) UHA-1 2.7 ND 0.054 ND ND 1.3 C2-S1 - ND UHA-2/2D 1.05 ND ND ND 0.050 0.9 C2-S1 - ND UHA-3/3S 0.94 ND ND/1.1 ND ND 1.6 C2-S1 - ND UHA-4 2.9 ND ND ND ND 0.7 C2-S1 - ND UHA-5 19 ND 0.054 ND ND 0.9 C3-S1 - ND UHA-6 ND ND 0.19 - 0.023 2.5 C4-S1 - ND UHA-7/7D 1.6 ND ND/.82 - 0.0285 2.5 C3-S1 - ND UHA-8/9 6.8 0.022 0.30 ND 0.035 2.2 C3-S1 - ND UHA-10 0.42 ND 0.059 ND ND 1.1 C2-S1 - ND UHA-11 12 ND 0.19 ND ND 1.8 C3-S1 - ND UHA-12 0.12 ND 0.062 ND 0.053 0.1 C2-S1 - ND UHA-13 1.2 ND ND ND 0.042 0.3 C2-S1 - ND UHA-15 1.6 ND ND ND 0.032 0.4 C2-S1 ND ND UHA-16 1.5 ND 0.095 ND 0.074 1.2 C2-S1 - ND UHA-17 0.24 ND 0.18 0.064 0.077 0.9 C2-S1 - ND UHA-18 0.40 ND 0.055 ND ND 1.2 C2-S1 - ND UHA-19/19S 11 ND 0.40/1 7 ND/0.68 ND 2.2 C4-S1 - ND UHA-20 0.85 ND ND ND ND 1.1 C3-S1 - ND UHA-21 11 ND 0.35 ND 0.16 1.5 C3-S1 - ND 2.15 ND 0.155 ND 0.0445 0.3 C2-S1 - ND UHA-23 2.9 ND 0.060 ND ND 0.4 C2-S1 - ND UHA-25 ND ND ND ND ND 0.6 C1-S1 - ND UHA-26 ND ND ND - 0.02 0.6 C3-S1 - - UHA-27 ND ND ND - 0.03 0.5 C2-S1 - - UHA-28 0.31 ND 0.13 - 0.02 0.6 C2-S1 - - UHA-29 0.15 ND 0.06 - ND 1.5 C2-S1 - - UHA-31 ND ND 0.10 - ND 2.0 C3-S1 - - UHA-32 1.7 ND ND ND 0.40 0.6 C3-S1 - - UHA-22/22D italics = constituent exceeded holding time 47 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009--Continued Site # Antimony (mg/L) Arsenic (mg/L) Barium (mg/L) Beryllium (mg/L) Boron (mg/L) Cadmium (mg/L) Chromium (mg/L) Copper (mg/L) Fluoride (mg/L) UHA-1 ND 0.010 ND ND 0.12 ND 0.035 ND 3.5 UHA-2/2D ND ND ND ND ND ND ND ND 0.41 UHA-3/3S ND ND ND ND ND ND 0.032 ND 0.41 UHA-4 ND ND ND ND ND ND ND ND 0.29 UHA-5 ND ND 0.22 ND ND ND ND ND 1.0 UHA-6 ND ND ND ND 0.19 ND ND ND 2.5 UHA-7/7D ND ND ND ND 0.14 ND ND ND/.011 2.35 UHA-8/9 ND ND 0.20 ND 0.105 ND ND 0.10 1.1 UHA-10 ND ND 0.24 ND ND ND ND ND 0.34 UHA-11 ND ND ND ND ND ND ND ND 1.6 UHA-12 ND ND ND ND ND ND ND 0.065 0.064 UHA-13 ND ND ND ND ND ND ND ND 0.12 UHA-15 ND ND ND ND ND ND ND ND 0.24 UHA-16 ND ND ND ND 0.12 ND ND 0.12 0.615 UHA-17 ND ND 0.43 ND ND ND ND ND 0.49 UHA-18 ND ND ND ND ND ND ND 0.017 2.4 UHA-19/19S ND ND 0.0.96 ND ND ND ND ND 1.2 UHA-20 ND ND ND ND ND ND ND ND 0.66 UHA-21 ND ND ND ND 0.20 ND ND ND 0.58 UHA-22/22D ND ND ND ND ND ND ND ND 0.25 UHA-23 ND ND 0.30 ND ND ND ND ND 0.30 UHA-25 ND ND ND ND ND ND ND ND 0.32 UHA-26 ND ND ND ND ND ND ND ND 0.65 UHA-27 ND ND ND ND ND ND ND ND 0.17 UHA-28 ND ND ND ND ND ND ND ND 0.62 UHA-29 ND ND ND ND ND ND ND ND 1.2 UHA-31 ND 0.0084 0.10 ND ND ND ND ND 0.54 UHA-32 ND ND 0.077 ND 0.13 ND ND ND 0.52 48 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009--Continued Site # Iron (mg/L) Lead (mg/L) Manganese (mg/L) Mercury (mg/L) Nickel (mg/L) Selenium (mg/L) Silver (mg/L) Thallium (mg/L) Zinc (mg/L) UHA-1 ND ND ND ND ND ND ND ND 0.077 UHA-2/2D ND ND ND ND ND ND ND ND ND UHA-3/3S ND ND ND ND ND ND ND ND 0.145 UHA-4 ND ND ND ND ND ND ND ND 0.78 UHA-5 ND ND ND ND ND ND ND ND 0.51 UHA-6 0.29 ND 1.5 ND ND ND ND ND 0.081 UHA-7/7D ND ND ND ND ND ND ND ND 3.45 UHA-8/9 ND ND ND ND 0.12/ND ND ND ND ND UHA-10 ND ND ND ND ND ND ND ND ND UHA-11 ND ND ND ND ND ND ND ND 0.56 UHA-12 ND ND ND ND ND ND ND ND ND UHA-13 ND ND ND ND ND ND ND ND 0.22 UHA-15 ND ND ND ND ND ND ND ND 0.13 UHA-16 ND ND ND ND 0.25/ND ND ND ND ND UHA-17 ND ND ND ND ND ND ND ND ND UHA-18 0.48 ND ND ND ND ND ND ND 2.2 UHA-19/19S ND ND ND ND ND ND/.0097 ND ND 1.1 UHA-20 ND ND ND ND ND ND ND ND 0.21 UHA-21 ND ND ND ND ND ND ND ND ND UHA-22/22D ND ND ND ND ND ND ND ND 0.41/ND UHA-23 ND ND ND ND ND ND ND ND ND UHA-25 ND ND ND ND ND ND ND ND ND UHA-26 0.29 ND 0.12 ND ND ND ND ND ND UHA-27 0.95 ND 0.063 ND ND ND ND ND ND UHA-28 ND ND ND ND ND ND ND ND 0.078 UHA-29 ND ND ND ND ND ND ND ND 0.20 UHA-31 ND ND 0.53 ND ND ND ND ND ND UHA-32 ND ND ND ND ND ND ND ND ND 49 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009--Continued Site # Radon-222 (pCi/L) Alpha (pCi/L) Beta (pCi/L) Ra-226 + Ra-228 (pCi/L) Uranium (µg/L) ∗18 O (0/00) ∗D (0/00) Type of Chemistry UHA-1 244 - - - - - 8.8 - 63 mixed-bicarbonate UHA-2/2D 229 - - - - - 8.3 - 61 calcium-bicarbonate UHA-3/3S 135 - - - - - 9.2 - 64 mixed-bicarbonate UHA-4 - 5.4 ND - - - 8.7 - 65 calcium-bicarbonate UHA-5 - 9.6 ND - - - 8.0 - 60 mixed-mixed UHA-6 - 41 ND - - - 8.7 - 62 mixed-sulfate UHA-7/7D - 42 ND - - - 10.0 - 71 mixed-bicarbonate UHA-8/9 218 2.5 ND ND - - 9.0 - 65 mixed-bicarbonate UHA-10 - 2.3 ND ND - - 10.2 - 72 calcium-bicarbonate UHA-11 - 30 ND ND - - 9.5 - 67 calcium-mixed UHA-12 - 3.4 ND ND - - 11.3 - 77 calcium-bicarbonate UHA-13 140 2.1 ND ND - - 11.4 - 78 calcium-bicarbonate UHA-14 - - - - - - 11.1 - 77 - UHA-15 - - - - - - 8.6 - 64 calcium-bicarbonate UHA-16 - - - - - - 9.1 - 65 mixed-bicarbonate UHA-16A - - - - - - 8.9 - 64 - UHA-17 < 47 - - - - - 9.4 - 67 calcium-bicarbonate UHA-18 - 75 6.5 ND - - 9.7 - 68 calcium-bicarbonate UHA-19/19S 547 - - - - - 8.8 - 65 calcium-chloride UHA-20 224 - - - - - 8.7 - 63 mixed-bicarbonate UHA-21 775 - - - - - 8.8 - 66 mixed-bicarbonate UHA-22/22D 276 - - - - - 7.3 - 61 calcium-bicarbonate UHA-23 - - - - - - 10.8 - 76 calcium-bicarbonate UHA-24 - - - - - - 9.9 - 73 - UHA-25 1186 - - - - - 10.8 - 76 calcium-bicarbonate UHA-26 1083 6.1 3.0 1.8 - - 10.9 - 77 calcium-bicarbonate UHA-27 - - - - - - 9.8 - 66 calcium-bicarbonate UHA-28 1412 6.6 8.2 ND - - 9.5 - 66 mixed-bicarbonate UHA-29 2641 20 8.4 ND 14 - 9.8 - 68 mixed-bicarbonate LLD = Lower Limit of Detection 50 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009---Continued Site # MCL Exceedances Temp (oC) pH-field (su) pH-lab (su) SC-field (µS/cm) SC-lab (µS/cm) TDS (mg/L) Hard (mg/L) Hard - cal (mg/L) Turb (ntu) UHA-33 - 8.7 7.49 8.0 530 500 310 200 210 1.2 UHA-35 Radon 15.1 7.18 8.0 719 700 430 300 300 0.01 UHA-36 TDS - 7.09 8.0 825 800 500 370 350 1.3 UHA-37 Radon 20.2 7.62 8.2 499 470 290 170 190 0.16 UHA-38 - 24.2 7.69 8.2 501 480 330 190 190 0.01 UHA-39 - 18.4 7.68 8.1 400 370 250 150 160 1.2 italics = constituent exceeded holding time Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009--Continued Site # Calcium (mg/L) Magnesium (mg/L) Sodium (mg/L) Potassium (mg/L) T. Alk (mg/L) Bicarbonate (mg/L) Carbonate (mg/L) Chloride (mg/L) Sulfate (mg/L) UHA-33 68 10 24 1.5 240 290 ND 15 4.2 UHA-35 82 22 33 1.2 260 320 ND 23 54 UHA-36 97 27 34 1.8 310 380 ND 24 68 UHA-37 40 23 24 1.8 180 220 ND 18 34 UHA-38 44 20 23 1.9 180 220 ND 13 48 UHA-39 54 5.6 13 2.2 150 180 ND 13 10 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009--Continued Site # Nitrate-N (mg/L) Nitrite-N (mg/L) TKN (mg/L) Ammonia (mg/L) T. Phosphorus (mg/L) SAR (value) Irrigation Quality Cyanide (ug/L) Aluminum (mg/L) UHA-33 ND ND 0.13 ND ND 0.7 C2-S1 - - UHA-35 2.9 ND ND ND ND 0.8 C2-S1 - - UHA-36 2.4 ND ND ND ND 0.8 C3-S1 - - UHA-37 1.3 ND ND ND ND 0.7 C2-S1 - - UHA-38 0.90 ND ND ND ND 0.7 C2-S1 - - UHA-39 3.6 ND ND ND ND 0.5 C2-S1 - - italics = constituent exceeded holding time 51 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009--Continued Site # Antimony (mg/L) Arsenic (mg/L) Barium (mg/L) Beryllium (mg/L) Boron (mg/L) Cadmium (mg/L) Chromium (mg/L) Copper (mg/L) Fluoride (mg/L) UHA-33 ND ND 0.011 ND ND ND ND ND 0.36 UHA-35 ND ND 0.050 ND 0.13 ND ND ND 0.46 UHA-36 ND ND 0.060 ND 0.12 ND ND ND 0.42 UHA-37 ND ND 0.022 ND ND ND 0.013 ND 0.51 UHA-38 ND 0.0062 0.021 ND ND ND ND ND 0.56 UHA-39 ND ND 0.018 ND ND ND ND ND 0.18 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009--Continued Site # Iron (mg/L) Lead (mg/L) Manganese (mg/L) Mercury (mg/L) Nickel (mg/L) Selenium (mg/L) Silver (mg/L) Thallium (mg/L) Zinc (mg/L) UHA-33 ND ND ND ND ND ND ND ND ND UHA-35 ND ND ND ND ND ND ND ND 0.050 UHA-36 ND ND ND ND ND ND ND ND ND UHA-37 ND ND ND ND ND ND ND ND ND UHA-38 ND ND ND ND ND ND ND ND ND UHA-39 ND ND ND ND ND ND ND ND 0.88 Appendix B. Groundwater Quality Data, Upper Hassayampa Basin, 2003-2009--Continued Site # Radon-222 (pCi/L) Alpha (pCi/L) Beta (pCi/L) Ra-226 + Ra-228 (pCi/L) Uranium (µg/L) ∗18 O (0/00) ∗D (0/00) Type of Chemistry UHA-30 - - - - - - 9.3 - 67 - UHA-31 - - - - - - 9.0 - 68 calcium-bicarbonate UHA-32 - 2.5 2.1 - - - 9.1 - 65 mixed-bicarbonate UHA-33 - - - - - - 9.4 - 67 calcium-bicarbonate UHA-34 - - - - - - 8.8 - 59 - UHA-35 320 - - - - - 9.5 - 67 calcium-bicarbonate UHA-36 - - - - - - 9.5 - 65 calcium-bicarbonate UHA-37 389 - - - - - 9.3 - 65 mixed-bicarbonate UHA-38 154 - - - - - 9.8 - 67 mixed-bicarbonate UHA-39 - - - - - - 10.0 - 69 calcium-bicarbonate LLD = Lower Limit of Detection 52