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Rare earth element behavior during groundwater – seawater mixing along the Kona Coast of Hawaii

Groundwater and seawater samples were collected from nearshore wells and offshore along the Kona Coast of the Big Island of Hawaii to investigate rare earth element (REE) behavior in local subterranean estuaries. Previous investigations showed that submarine groundwater discharge (SGD) is the predominant flux of terrestrial waters to the coastal ocean along the arid Kona Coast of Hawaii. Groundwater and seawater samples were filtered through 0.45 μm and 0.02 μm pore-size filters to evaluate the importance of colloidal and soluble (i.e., truly dissolved ionic species and/or low molecular weight [LMW] colloids) fractions of the REEs in the local subterranean estuaries. Mixing experiments using groundwater collected immediately down gradient from a wastewater treatment facility (WWTF) proximal to the Kaloko-Hanokohau National Historic Park, and more “pristine” groundwater from a well constructed in a lava tube at Kiholo Bay, were mixed with local seawater to study the effect of solution composition (i.e., pH, salinity) on the concentrations and fractionation behavior of the REEs as groundwater mixes with seawater in Kona Coast subterranean estuaries. The mixed waters were also filtered through 0.45 or 0.02 μm filters to ascertain the behavior of colloidal and soluble fractions of the REEs across the salinity gradient in each mixing experiment. Concentrations of the REEs were statistically identical (two-tailed Student t -test, 95% confidence) between the sequentially filtered sample aliquots, indicating that the REEs occur as dissolved ionic species and/or LMW colloids in Kona Coast groundwaters. The mixing experiments revealed that the REEs are released to solution from suspended particles or colloids when Kona Coast groundwater waters mix with local seawater. The order of release that accompanies increasing pH and salinity follows light REE (LREE) > middle REE (MREE) > heavy REE (HREE). Release of REEs in the mixing experiments is driven by decreases in the free metal ion activity in solution and the concomitant increase in the amount of each REE that occurs in solution as dicarbonato complexes [i.e., Ln(CO 3 ) 2 - ] as pH increases across the salinity gradient. Input-normalized REE patterns of Kona Coast groundwater and coastal seawater are nearly identical and relatively flat compared to North Pacific seawater, indicating that SGD is the chief source of these trace elements to the ocean along the Kona Coast. Additionally, REE concentrations of the coastal seawater are between 10 and 50 times higher than previously reported open-ocean seawater values from the North Pacific, further demonstrating the importance of SGD fluxes of REEs to these coastal waters. Taken together, these observations indicate that large-scale removal of REEs, which characterizes the behavior of REEs in the low salinity reaches of many surface estuaries, is not a feature of the subterranean estuary along the Kona Coast. A large positive gadolinium (Gd) anomaly characterizes groundwater from the vicinity of the WWTF. The positive Gd anomaly can be traced to the coastal ocean, providing further evidence of the impact of SGD on the coastal waters. Estimates of the SGD fluxes of the REEs to the coastal ocean along the Kona Coast (i.e., 1.3 – 2.6 mmol Nd day -1 ) are similar to recent estimates of SGD fluxes of REEs along Florida’s east coast and to Rhode Island Sound, all of which points to the importance of SGD as significant flux of REEs to the coastal ocean.

Hawaii

Numerical simulation of the groundwater-flow system in Chimacum Creek Basin and vicinity, Jefferson County, Washington

A groundwater-flow model was developed to evaluate potential future effects of growth and of water-management strategies on water resources in the Chimacum Creek Basin. The model covers an area of about 64 square miles (mi 2 ) on the Olympic Peninsula in northeastern Jefferson County, Washington. The Chimacum Creek Basin drains an area of about 53 mi 2 and consists of Chimacum Creek and its tributary East Fork Chimacum Creek, which converge near the town of Chimacum and discharge to Port Townsend Bay near the town of Irondale. The topography of the model area consists of north-south oriented, narrow, regularly spaced parallel ridges and valleys that are characteristic of fluted glaciated surfaces. Thick accumulations of peat occur along the axis of East Fork Chimacum Creek and provide rich soils for agricultural use. The study area is underlain by a north-thickening sequence of unconsolidated glacial (till and outwash) and interglacial (fluvial and lacustrine) deposits, and sedimentary and igneous bedrock units that crop out along the margins and the western interior of the model area. Six hydrogeologic units in the model area form the basis of the groundwater-flow model. They are represented by model layers UC (upper confining), UA (upper aquifer), MC (middle confining), LA (lower aquifer), LC (lower confining), and OE (bedrock). Groundwater flow in the Chimacum Creek Basin and vicinity was simulated using the groundwater-flow model, MODFLOW-2005. The finite-difference model grid comprises 245 columns, 313 rows, and 6 layers. Each model cell has a horizontal dimension of 200 × 200 feet (ft). The thickness of model layers varies throughout the model area and ranges from 5 ft in the non-bedrock units to more than 2,400 ft in the bedrock. Groundwater flow was simulated for steady-state conditions, which were simulated for calibration of the model using average recharge, discharge, and water levels for the 180-month period October 1994–September 2009. The model as calibrated has a mean residual of 4.5 ft and a standard error on the mean of 2.1 ft for heads, and 0.64±0.42 cubic feet per second for streamflows. After the model was calibrated, a Current Conditions simulation was developed to reflect current (October 2008–September 2009) hydrologic conditions, with representative pumping, return flows, and “normal” recharge (based on National Weather Service average precipitation for 1981 to 2010). The Current Conditions simulation was used to estimate current flow quantities, and as a basis to compare other simulations.Simulated steady-state inflow to the model area from precipitation and secondary recharge, or “return flow,” was 16,347 acre-feet per year (acre-ft/yr); groundwater inflow from other basins to the north of the model boundary was 1,518 acre-ft/yr (net, 3,114 acre-ft/yr in and 1,596 acre-ft/yr out) and simulated inflow from lake leakage was 613 acre-ft/yr (net, 684 acre-ft/yr in and 71 acre-ft/yr out). Simulated outflow from the model primarily was through discharge to Puget Sound (10,022 acre-ft/yr), streams (5,424 acre-ft/yr ), springs and seeps (1,521 acre-ft/yr), and through withdrawals from wells (1,506 acre-ft/yr). Four simulations were formulated using the calibrated model—one to represent current conditions (2009, the end of the period used for calibration) and three to provide representative examples of how the model can be used to evaluate the relative effects of potential changes in groundwater withdrawals and consumptive use on groundwater levels and stream base flows: Probable Future Use, based on population projections; Full Beneficial Use, based on Jefferson County Public Utility District #1 water rights; Sanitary Sewer, based on eliminating septic return flows in the Urban Growth Area. Particle tracking was used to assess flowpaths from sources and to sinks, and the effects of the presence of irrigation wells and their depths was assessed.

Washington

Estimated water use and availability in the South Coastal Drainage Basin, southern Rhode Island, 1995-99

The South Coastal Drainage Basin includes approximately 59.14 square miles in southern Rhode Island. The basin was divided into three subbasins to assess the water use and availability: the Saugatucket, Point Judith Pond, and the Southwestern Coastal Drainage subbasins. Because there is limited information on the ground-water system in this basin, the water use and availability evaluations for these subbasins were derived from delineated surface-water drainage areas. An assessment was completed to estimate water withdrawals, use, and return flow over a 5-year study period from 1995 through 1999 in the basin. During the study period, one major water supplier in the basin withdrew an average of 0.389 million gallons per day from the sand and gravel deposits. Most of the potable water is imported (about 2.152 million gallons per day) from the adjacent Pawcatuck Basin to the northwest. The estimated water withdrawals from the minor water suppliers, which are all in Charlestown, during the study period were 0.064 million gallons per day. The self-supplied domestic, industrial, commercial, and agricultural withdrawals from the basin were 0.574 million gallons per day. Water use in the basin was 2.874 million gallons per day. The average return flow in the basin was 1.190 million gallons per day, which was entirely from self-disposed water users. In this basin, wastewater from service collection areas was exported (about 1.139 million gallons per day) to the Narragansett Bay Drainage Basin for treatment and discharge. During times of little to no recharge, in the form of precipitation, the surface- and ground-water system flows are from storage primarily in the stratified sand and gravel deposits, although there is flow moving through the till deposits at a slower rate. The ground water discharging to the streams, during times of little to no precipitation, is referred to as base flow. The PART program, a computerized hydrograph-separation application, was used at the selected index stream-gaging station to determine water availability based on the 75th, 50th, and 25th percentiles of the total base flow, the base flow minus the 7-day, 10-year flow criteria, and the base flow minus the Aquatic Base Flow criteria at the index station. The base flow calculated at the selected index station was subdivided into two rates on the basis of the percent contributions from sandand-gravel and till deposits. There has been no long-term collection of surface-water data in this study area and therefore an index stream-gaging station in the Pawcatuck Basin was used for the South Coastal Drainage Basin. The Pawcatuck River at Wood River Junction was chosen as the index station for the South Coastal Drainage Basin because the station is representative of the basin on the basis of the percentage of sand and gravel deposits and the average extent of thickness of the sand and gravel deposits. The baseflow contributions from sand and gravel deposits at the index station were computed for June, July, August, and September, and applied to the percentage of surficial deposits at the index station. The base-flow contributions were converted to a per unit area at the station for the till, and for the sand and gravel deposits and applied to the South Coastal Drainage Basin to determine the water availability. The results from the index station, the Pawcatuck River at Wood River Junction streamgaging station, were lowest for the summer in September. To determine water availability in the South Coastal Drainage Basin, the per unit area of the estimated base flows from sand and gravel deposits and till deposits at the index station was applied to the subbasin areas, and the resultant flows were lowest in September. The base flow at the 75th percentile in the basin was 56.95 million gallons per day in June; 32.78 million gallons per day in July; 30.22 million gallons per day in August; and 23.94 million gallons per day in September. The base flow at the 50th percentile in the basin was 44.59 million gallons per day in June; 25.31 million gallons per day in July; 20.75 million gallons per day in August; and 17.01 million gallons per day in September. The base flow at the 25th percentile in the basin was 35.52 million gallons per day in June; 20.40 million gallons per day in July; 14.94 million gallons per day in August; and 12.00 million gallons per day in September. There are some limitations in the application of this method along the coast, because saltwater intrusion can change the amount of fresh ground-water discharge to the coastal saltwater ecosystem. A ground-water system analysis evaluating these variances would provide additional information to assess the water availability along the coast. Because water withdrawals and use are greater during the summer than other times of the year, water availability in June, July, August, and September was assessed and compared to water withdrawals in the basin. The ratios were calculated by dividing the water withdrawals by the water-availability flow scenarios at the 75th, 50th, and 25th percentiles for the basin, which are based on total water available from base-flow contributions from till and sand and gravel deposits in the basin. The closer the ratio is to one, the closer the withdrawals are to the estimated water available, and the net water available decreases. For the study period, the withdrawals in July were higher than the other summer months. The ratios in the basin for the base-flow scenario, with no low-flow criteria removed, ranged from 0.029 to 0.046 in June; 0.059 to 0.094 in July; 0.050 to 0.100 in August; and 0.040 to 0.079 in September. A long-term hydrologic budget (60 years) was calculated for the South Coastal Drainage Basin to identify and assess the basin and subbasin inflow and outflows. This coastal basin is different than other study areas because all three of the subbasins drain into salt water, Point Judith Point, Long Island Sound, and Rhode Island Sound towards the Atlantic Ocean, or internally within the subbasin to the salt ponds. The hydrologic budgets, therefore, were compiled by subbasin. The basin hydrologic budget is the sum of the three subbasin budgets. Unlike a river subbasin drainage system, however, the estimated streamflows out of the subbasins were also considered outflows from the basin. The water withdrawals and return flows used in the budget were from 1995 through 1999. For the hydrologic budget, it was assumed that inflow equals outflow, where the estimated inflows were from precipitation and wastewater-return flow, and the estimated outflows were from evapotranspiration, streamflow, and water withdrawals.

Rhode Island