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In 2008, the Mulberry River, a National Wild and Scenic River, was listed as impaired due to low pH (below pH 6.0). Over the last 50 years, the volume of conifers in the Ozark region has increased 115% since 1978 which may result in the acidification of nearby aquatic ecosystems. The objective of this study was to determine if differences exist in soil and litter chemical properties between deciduous and coniferous tree stands. Aboveground litter (n = 200) and soil (n = 400) at 0- to 5- and 5- to 15-cm depths were collected at paired deciduous and coniferous stands at 10 locations within the Mulberry River watershed and analyzed for a suite of chemical parameters. There were no differences (P 0.05) in several measures of soil acidity between deciduous and coniferous stands. Litter collected from the coniferous stands was more acidic than deciduous litter (4.4 vs 4.7; P 0.05). Cation exchange capacity, exchangeable Ca and Mg, and water-soluble P and Mg contents differed (P 0.05) by stand and depth. Cation exchange capacity and exchangeable Ca and Mg were greatest in the 0- to 5-cm depth interval of the coniferous stands. Water-soluble P and Mg contents were greatest within the 0- to 5-cm depth interval which did not differ (P 0.05) between stand but were greater than the 5- to 15-cm depth interval. Although limited to the top 15-cm of soil, the similarity in soil acidity between stands suggests that conifer growth may not be a substantial source of acidity to the Mulberry River.

The nature of carbon (C) cycling in the unsaturated zone where groundwater is in contact with abundant gas-filled voids is poorly understood. The objective of this study was to trace inorganic-C cycling in a karst landscape using stable-C isotopes, with emphasis on a shallow groundwater flow path through the soil, to an underlying cave, and to the spring outlet of a cave stream in the Ozark Plateaus of northwestern Arkansas. Carbon dioxide (CO2) concentration and isotopic composition (δ13C-CO2) in gas and dissolved inorganic carbon (DIC) concentration and isotopic composition (δ13C-DIC) in water were measured in samples collected from two suction-cup soil samplers above the cave, three sites in the cave, and at the spring outlet of the cave stream. Soil-gas CO2 concentration (median 2,578 ppm) and δ13C-CO2 (median − 21.5‰) were seasonally variable, reflecting the effects of surface temperature changes on soil-CO2 production via respiration and organic-matter decomposition. Cave-air CO2 (median 1,026 ppm) was sourced from the soil zone and the surface atmosphere, with seasonally changing proportions of each source controlled by surface temperature-driven air density gradients. Soil-DIC concentration (median 1.7 mg L− 1) was lower and soil-δ13C-DIC (median − 19.5‰) was lighter compared to the cave (median 23.3 mg L− 1 and − 14.3‰, respectively) because carbonate-bedrock dissolution provided an inorganic source of C to the cave. Carbon species in the soil had a unique, light stable-C isotopic signature compared to the cave. Discrimination of soil-C sources to karst groundwater was achieved, which is critical for developing hydrologic budgets using environmental tracers such as C.

The Phosphorus (P) Index risk assessment tool has been widely adopted across the United States to identify and rank site vulnerability to P runoff as part of the Natural Resources Conservation Service nutrient management planning (NMP) process. However, limited success has been achieved in addressing the risk of P loss by subsurface flow pathways, despite its relative importance in certain areas of the United States, particularly in those U.S. states dominated by karst terrain. Here we review how states with varying land areas classified as having karst features address the risk of P runoff during the NMP process. Indices adopted in Illinois and Indiana require setbacks (widths 15–72 m) around surface karst features. The remaining states with karst address the risk of P loss in NMP development rather than the application of a P Index. Given the spatially variable hydrogeologic properties of karst, technically rigorous field‐scale factors are unlikely to be developed in the near future.

Isotopes—atoms of the same chemical element with varying mass and behavior—are used widely in cave research to understand modern and ancient karst systems. Radioisotopes decay spontaneously, and their well-defined decay rates are used for age dating water and materials in caves. Stable isotopes, which do not decay, are used to study modern karst including distinguishing sources of cave air, water, and contaminants and to study past climates and environments through interpretations of isotopes preserved in cave formations (speleothems) and sediments. Radioisotopes used in cave research include carbon-14 in charcoal or bones, uranium-234 and thorium-230 in speleothems, aluminum/beryllium ratios of quartz sediment transported into caves, and tritium and chlorine-36 in karst waters. Stable isotopes used to study caves include oxygen and hydrogen isotopes of water, inorganic carbon (both dissolved and bound in calcite of bedrock or speleothems), and possible contaminants in water, such as nitrate and sulfate.

Instream biogeochemical process measurements are often short-term and localized. Here we use in situ sensors to quantify the net effects of biogeochemical processes on seasonal patterns in baseflow nitrate retention at the river-reach scale. Dual-station high-frequency in situ nitrate measurements, were coupled with high-frequency measurements of stream metabolism and dissolved inorganic carbon, in a tributary of the Buffalo National River, Arkansas. Nitrate assimilation was calculated from net primary production, and combined with mass-balance measurements, to estimate net nitrification and denitrification. The combined net effects of these instream processes (assimilation, denitrification, and nitrification) removed >30–90% of the baseflow nitrate load along a 6.5 km reach. Assimilation of nitrate by photoautotrophs during spring and early summer was buffered by net nitrification. Net nitrification peaked during the spring. After midsummer, there was a pronounced switch from assimilatory nitrate uptake to denitrification. There was clear synchronicity between the switch from nitrate assimilation to denitrification, a reduction in river baseflows, and a shift in stream metabolism from autotrophy to heterotrophy. The results show how instream nitrate retention and downstream delivery is driven by seasonal shifts in metabolic pathways; and how continuous in situ stream sensor networks offer new opportunities for quantifying the role of stream biota in the dynamics, fate, and transport of nitrogen in fluvial systems.

Fig. 1. was amended to reduce the size of the map and improve formatting of the manuscript. The authors claim this amendment does not affect the information being conveyed.

In northwestern Arkansas, karst aquifers have experienced degraded water quality due to impacts of land-use changes, such as increased urbanization or intensification of agriculture. Water quality at a karst spring was characterized by quantifying the variability of fecal-indicator bacteria, specifically Escherichia coli (E. coli), throughout base-flow periods and storm events. Water-quality change over time was assessed using an intermittent record of nitrate and chloride data since the 1990s. A Geographic Information System was used to quantify changes in land use over time and identify housing subdivisions using on-site septic systems. E. coli was significantly greater during storm events (649 CFU/100 mL or MP/100 mL) than base-flow periods (41 CFU/100 mL or MPN/100 mL). The increase in E. coli at the spring following storm events was interpreted to result from flushing of bacteria from the land surface, through the epikarst and karst conduits, and into groundwater. Nitrate and chloride have increased significantly since the 1990s, following the general pattern of increased urbanization in the recharge area. Septic-tank effluent may be degrading the water quality of the karst spring based on the dominance of on-site septic tank usage in the recharge area, unsuitable topography and soil type for septic tank absorption fields, increased nitrate and chloride concentrations concomitant with increased urbanization, and increase of the fecal-indicator bacteria E. coli following storm events.

Nutrient concentrations in several streams of the Boston and Ozark Mountains region of Arkansas, including the Buffalo National River and its tributaries, have garnered tremendous interest. In particular, Big Creek has been the center of attention within the Buffalo River watershed because of a permitted concentrated animal feeding operation (CAFO). The objectives of this paper were to put nutrient concentrations of Big Creek into the context of the stream nutrient and watershed land-use relationship and develop a framework to evaluate regional land-use impacts on regional water quality. Nutrient concentrations in streams draining the Boston and Ozark Mountains region were related to the intensity of watershed land use. Concentrations in Big Creek were similar to other watersheds in the ecoregion with similar land use, suggesting limited impact of the CAFO on Big Creek at the present time. However, this does not preclude future impacts, and longer-term monitoring continues.

Optimal utilization of animal manures as a plant nutrient source should also prevent adverse impacts on water quality. The objective of this study was to evaluate long-term poultry litter and N fertilizer application on nutrient cycling following establishment of an alley cropping system with eastern black walnut (Juglans nigra L.), pecan [Carya illinoensis (Wangenh.) K. Koch], and northern red oak (Quercus rubra L.) trees and orchardgrass (Dactylis glomerata L.). One half of a 4.25-ha site in northwestern Arkansas USA received broadcast applications of 3.9–6.7 Mg ha−1 fresh poultry litter and the other half 50–76 kg ha−1 N as NH4NO3 fertilizer each spring from 2001 to 2008. Macronutrient (N, P, K, Ca, Mg, and S) and micronutrient (Na, Fe, Mn, Zn, and Cu) concentrations in soil, forage, and tree leaf tissue were monitored along with NO3-N in soil water and groundwater. Poultry litter application resulted in significantly increased concentrations of each macronutrient except S with increases from 6.3 (N) to 121 % (P). Nitrogen fertilizer application resulted in decreased concentrations from 2.1 (N) to 60.9 % (S) for all macronutrients except Ca. Patterns of nutrient content in forage and tree leaf tissue did not generally follow patterns of soil nutrient concentrations suggesting nutrient sufficiency in most years and that climate and plant growth had a greater effect on nutrient uptake. Soil P with litter application increased 41.3 mg kg−1 over 7 years (from 34.1 to 75.4), which may necessitate a lower litter application rate to avoid excessive P runoff.

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH4 gas content and its C isotopes (δ13CCH4), and select isotope tracers (δ11B, 87Sr/86Sr, δ2H, δ18O, δ13CDIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH4 was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5mg CH4/L. The δ13CCH4 of dissolved CH4 ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH4 concentrations, with a possible minor contribution of trace amounts of thermogenic CH4. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ13CCH4=−35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (100mg/L and Ca–HCO3 dominated, (3) TDS>100mg/L and Na–HCO3 dominated, and (4) slightly saline groundwater with TDS>100mg/L and Cl>20mg/L with elevated Br/Cl ratios (>0.001). The Sr (87Sr/86Sr=0.7097–0.7166), C (δ13CDIC=−21.3‰ to −4.7‰), and B (δ11B=3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO3, and higher-mineralized Na–HCO3 composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH4 and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.

average values for d 26 Mg= � 0.832 � 0.068 and d 25 Mg= � 0.432 � 0.053 (n=40, 2SD) – identical to those of seawater from Hawaii (average d 26 Mg= � 0.829 � 0.037 and d 25 Mg= � 0.427 � 0.033) and to the average literature values of seawater worldwide (d 26 Mg= � 0.83 � 0.11 and d 25 Mg= � 0.43 � 0.06, n=49, 2SD). Collectively, global seawater has a homogeneous Mg isotopic composition with d 26 Mg= � 0.83 � 0.09 and d 25 Mg= � 0.43 � 0.06 (2SD, n=90). The magnesium isotopic composition of seawater is principally controlled by river water input, carbonate precipitation and oceanic hydrothermal interactions. The homogeneous Mg isotopic composition of seawater indicates a steady-state budget in terms of Mg isotopes in oceans, consistent with a long Mg residence time (~13 Ma). Considering that seawater is homogeneous, readily available in large amounts, can be easily accessed and processed for isotopic analysis, and has an isotopic composition near the middle of the natural range of variation, it is an excellent geostandard for accuracy assessment to rule out analytical artifacts during high-precision Mg isotopic analysis. Copyright © 2011 John Wiley & Sons, Ltd.

The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6 m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21–36.6 m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory.

The magnesium (Mg) isotopic compositions of 40 seawater samples from the Gulf of Mexico and of one seawater sample from the southwest Hawaii area were determined by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) to investigate the homogeneity of Mg isotopes in seawater. The results indicate that the Mg isotopic composition of seawater from the Gulf of Mexico is homogeneous, both vertically and horizontally, with average values for δ(26)Mg = -0.832 ± 0.068 and δ(25)Mg = -0.432 ± 0.053 (n = 40, 2SD)--identical to those of seawater from Hawaii (average δ(26)Mg = -0.829 ± 0.037 and δ(25)Mg = -0.427 ± 0.033) and to the average literature values of seawater worldwide (δ(26)Mg = -0.83 ± 0.11 and δ(25)Mg = -0.43 ± 0.06, n = 49, 2SD). Collectively, global seawater has a homogeneous Mg isotopic composition with δ(26)Mg = -0.83 ± 0.09 and δ(25) Mg = -0.43 ± 0.06 (2SD, n = 90). The magnesium isotopic composition of seawater is principally controlled by river water input, carbonate precipitation and oceanic hydrothermal interactions. The homogeneous Mg isotopic composition of seawater indicates a steady-state budget in terms of Mg isotopes in oceans, consistent with a long Mg residence time (~13 Ma). Considering that seawater is homogeneous, readily available in large amounts, can be easily accessed and processed for isotopic analysis, and has an isotopic composition near the middle of the natural range of variation, it is an excellent geostandard for accuracy assessment to rule out analytical artifacts during high-precision Mg isotopic analysis.

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (

Because meteoric water δ 18 O values decrease with decreasing ambient temperature and increasing latitude, δ 18 O values of meteoric calcite cement should exhibit a similar relation with paleolatitude and be an indicator of continental paleotemperatures. To test this, we compiled isotopic and paleolatitude data for 20 meteoric cements and nine speleothems ranging in age from Devonian to modern and in paleolatitude from 3.5° to 83°. Mean δ 18 O values for meteoric cements and speleothems both show the same negative correlation with paleolatitude. The δ 18 O vs. latitude trend for these carbonates is almost identical to that predicted for modern inland environments, but differs from the trend for coastal environments. This suggests that the ground water controlling the ultimate composition of meteoric cement is derived predominantly from inland recharge. If it is assumed that the modern meteoric water δ 18 O vs. temperature relation is valid for the past and that insignificant evaporation occurred prior to carbonate precipitation, then coastal and inland paleotemperatures can be calculated from the δ 18 O values of meteoric calcite (δ 18 O mcl ) and seawater (δ 18 O sw ) by using the equations T coastal =13.3 ±32.6[-0.231- 0.0613(δ 18 O mcl + δ 18 O sw ) ½ and T inland =17.8 ±16.2[-0.572 - 0.1233(δ 18 O mcl + δ 18 O sw ) ½ , where T is temperature in °C. Calcite precipitated from coastal meteoric water at temperatures between 0 and 25 °C will exhibit a narrow range in δ 18 O(-6‰ to -4‰, where δ 18 O sw = 0‰). The δ 18 O of calcite precipitated from inland meteoric water will be sensitive to paleotemperature, ranging from -14‰ to -5‰ (where δ 18 O sw = 0‰) for temperatures of 0 to 25 °C.