MODELING ACID MINE DRAINAGE ON A WATERSHED SCALE FOR TMDL CALCULATIONS1

ABSTRACT: The Cheat River of West Virginia is impaired by acid mine drainage (AMD). Fifty‐five of its river segments were placed on the 303(d) list, which required calculations of total maximum daily load (TMDL) to meet the water quality criteria for pH, total iron, aluminum, manganese, and zinc. An existing watershed model was enhanced to simulate AMD as nonpoint source load. The model divided a watershed into a network of catchments and river segments. Each catchment was divided into soil layers, which could contain pyrite, calcite and other minerals. A kinetic expression was used to simulate pyrite oxidation as a function of oxygen in the soil voids. Oxygen in the soil voids was consumed by pyrite oxidation and replenished by earth breathing. The by‐products of pyrite oxidation were calculated according to its mass action equations. Chemical equilibrium was used to account for the speciation of ferrous and ferric irons and precipitation of metal hydroxides. Simulated hydrology and water quality were compared to available data. The USEPA used the calibrated model to calculate the TMDLs in the Cheat River Watershed.     

In Situ treatment of PFAS‐impacted groundwater using colloidal activated Carbon

Poly‐ and perfluoroalkyl substances (PFASs) have been identified by many regulatory agencies as contaminants of concern within the environment. In recent years, regulatory authorities have established a number of health‐based regulatory and evaluation criteria with groundwater PFAS concentrations typically being less than 50 nanograms per liter (ng/L). Subsurface studies suggest that PFAS compounds are recalcitrant and widespread in the environment. Traditionally, impacted groundwater is extracted and treated on the surface using media such as activated carbon and exchange resins. These treatment technologies are generally expensive, inefficient, and can take decades to reach treatment objectives. The application of in situ remedial technologies is common for a wide variety of contaminants of concern such as petroleum hydrocarbons and volatile organic compounds; however, for PFASs, the technology is currently emerging. This study involved the application of colloidal activated carbon at a site in Canada where the PFASs perfluorooctanoate (PFOA) and perfluorooctane sulfonic acid (PFOS) were detected in groundwater at concentrations up to 3,260 ng/L and 1,450 ng/L, respectively. The shallow silty‐sand aquifer was anaerobic with an average linear groundwater velocity of approximately 2.6 meters per day. The colloidal activated carbon was applied using direct‐push technology and PFOA and PFOS concentrations below 30 ng/L were subsequently measured in groundwater samples over an 18‐month period. With the exception of perfluoroundecanoic acid, which was detected at 20 ng/L and perfluorooctanesulfonate which was detected at 40 ng/L after 18 months, all PFASs were below their respective method detection limits in all postinjection samples. Colloidal activated carbon was successfully distributed within the target zone of the impacted aquifer with the activated carbon being measured in cores up to 5 meters from the injection point. This case study suggests that colloidal activated carbon can be successfully applied to address low to moderate concentrations of PFASs within similar shallow anaerobic aquifers.     

Chemical oxidation using stabilized hydrogen peroxide in high temperature,saline groundwater impacted with hydrocarbons and MTBE

In situ chemical oxidation (ISCO) of petroleum hydrocarbons (PHCs) within groundwater is considered a proven approach to addressing PHC‐impacted groundwater in nonsaline environments. One of the most common oxidants used for oxidation of PHCs in groundwater is hydrogen peroxide (H₂O₂). Due to its highly reactive nature, H₂O₂ is often stabilized to aid in increasing its reactivity lifespan. Limited research and application of ISCO has been completed in warm, saline groundwater environments. Furthermore, even fewer studies have been completed in these environments for ISCO using stabilized H₂O₂. In this research, stabilized H₂O₂ was examined to determine its effectiveness in the treatment of PHCs and the additive methyl tert‐butyl ether (MTBE). Three stabilizers (citrate, phytate, silica [SiO₂]) were tested to determine if the stabilizers could enhance and extend the treatment life of H₂O₂ within saline groundwater. To determine the effect of salinity on the three stabilizers, groundwater and aquifer samples were collected from two saline locations that had different salinity (total dissolved solids of about 7,000 mg/L and 18,000 mg/L). Specific target chemicals for treatment were water soluble, mobile components of gasoline including benzene, toluene, ethylbenzene, xylenes, (BTEX) and MTBE. Previous studies using unactivated persulfate indicated that the PHCs within the groundwater could be oxidized, however, only limited oxidation of the MTBE could be affected. The results of the laboratory tests indicated that greater than 95 percent of the target hydrocarbons were removed within 7 days of treatment. Microcosms with citrate‐stabilized H₂O₂ demonstrated a significantly faster and greater decline with most hydrocarbon concentrations reaching < 5 μg/L. The exceptions were ethylbenzene and m‐xylene, which were slightly decreased to about 30 and 20 μg/L, respectively. Initial mean concentrations of the BTEX compounds within the citrate‐stabilized microcosms were 10,554 μg/L, 9,318 μg/L, 6,859 μg/L, and 14,435 μg/L, respectively. The silicate‐stabilized H₂O₂ microcosms showed no significant benefit over the unstabilized control microcosms. The better performance of citrate‐stabilized microcosms was confirmed by increasing δ13C values of remaining hydrocarbons. MTBE declined from > 400 mg/L to < 100 mg/L in all microcosms, again with the best removal (> 90 percent) being measured in the citrate‐stabilized microcosms. Unfortunately, H₂O₂ oxidation in the microcosms also resulted in production of up to 40 mg/L TBA or approximately 10 percent of the MTBE oxidized.     

The in situ treatment of PFAS within porewater at the air–water interface of a PFAS source zone

The treatment of per- and polyfluoroalkyl substances (PFAS) within groundwater is an emerging topic, with various technologies being researched and tested. Currently, PFAS-impacted groundwater is typically treated ex situ using sorptive media such as activated carbon and ion exchange resin. Proven in situ remedial approaches for groundwater have been limited to colloidal activated carbon (CAC) injected into aquifers downgradient of the source zones. However, treatment of groundwater within the source zones has not been shown to be feasible to date. This study evaluated the use of CAC to treat dissolved PFAS at the air–water interface within the PFAS source zone. Studies have shown that PFAS tends to preferentially accumulate at the air–water interface due to the chemical properties of the various PFAS. This accumulation can act as a long-term source for PFAS, thus making downgradient treatment of groundwater a long-term requirement. A solution of CAC was injected at the air–water interface within the source zone at a site with PFAS contamination using direct push technology. A dense injection grid that targeted the interface between the air and groundwater was used to deliver the CAC. Concentrations of PFAS within the porewater and groundwater were collected using a series of nine lysimeters installed within the vadose and saturated water columns. A total of six PFAS were detected in the porewater and groundwater including perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA). Detectable concentrations of PFAS within the pore and groundwater before treatment ranged from values greater than 300 µg/L for PFPeA to less than 3 µg/L for PFNA. Following the injection of the CAC, monitoring of the porewater and groundwater for PFAS was conducted approximately 3, 6, 9, 12, and 18 months postinjection. The results indicated that the PFAS within the porewater and groundwater at and near the air–water interface was effectively attenuated over the 1.5-year monitoring program, with PFAS concentrations being below the method detection limits of approximately 10 ng/L, with the exception of PFPeA, which was detected within the porewater during the 18-month sampling event at concentrations of up to 55 ng/L. PFPeA is a five carbon-chained PFAS that has been shown to have a lower affinity for sorption onto activated carbon compared to the longer carbon-chained PFAS such as PFOA. Examination of aquifer cores in the zone of injection indicated that the total organic carbon concentration of the aquifer increased by five orders of magnitude postinjection, with 97% of the samples collected within the target injection area containing activated carbon, indicating that the CAC was successfully delivered into the source zone.     

Toxicity and metal speciation characterisation of waste water from an abandoned gold mine in tropical northern Australia

The decommissioned Mount Todd gold mine, located in the wet-dry tropics of northern Australia, consists of a large waste water inventory and an acid rock drainage problem, which has the potential to impact upon freshwater ecosystems of the Edith River catchment. The toxicity of retention pond 1 (RP1) water was determined using six local freshwater species (duckweed, alga, cladoceran, snail, hydra and a fish). RP1 water was very toxic to all species, with the percentage dilution of RP1 water inhibiting 10% of organism response (IC(10)), or lethal to 5% of individuals (LC(5)), ranging from 0.007 to 0.088%. The percentage dilution of RP1 water inhibiting 50% of organism response (IC(50)), or lethal to 50% of individuals (LC(50)), ranged from 0.051% to 0.58%. Based on chemical analyses and geochemical speciation modelling of the test waters, Cu, Zn and Al were the most likely toxic components at acidic dilutions (i.e. 1%), while Cu and Zn were the most likely toxic components at 0.1% RP1 water, where pH was 6.5. Species sensitivity distributions (SSDs) were used to predict dilutions of RP1 water that would protect or unacceptably affect the downstream aquatic ecosystems. A dilution ratio of 1 part RP1 water to 20000 parts Edith River water (0.005% RP1 water) was calculated to be required for the protection of at least 95% of species. This information can be used in conjunction with field chemical and biological data to better predict the ecological risks of RP1 waste water downstream of the Mount Todd mine.     

The experiences of four corporate officials managing compliance with the Massachusetts Toxics Use Reduction Act

The Massachusetts Toxics Use Reduction Act (TURA), one of the original pollution prevention laws, has faced repeated repeal attempts and budget cuts. Yet the Massachusetts toxics use data and other analyses have provided firm indications that the law has actually worked. Though the program has survived it is notable that an approach that both saves money and reduces pollution has been reduced and not expanded. This paper does not attempt to answer the question of why the strategies of TURA have not seen wider application, but offers four stories to illustrate what happens when they are properly applied. The experience of corporate officials who had to comply with TURA, related at a symposium on the occasion of the law’s 20th anniversary, shed light on how a strong pollution prevention law can benefit regulated companies as well as the environment and worker and public health, and provide suggestions, in addition to data and surveys, that TURA-like sets of governance tools should receive wider consideration.     

History and Development of the NRCS Lag Time Equation1

Abstract: Many of the hydrologic methods that are used in engineering practice today resulted from the Spring Flood of 1936, which blanketed the Northeastern portion of the United States. Because of the flood damage that was caused by this rainfall‐snowmelt event, many federal agencies including the U.S. Army Corp of Engineers and the Soil Conservation Service (SCS) implemented the hydrologic theories that were available in the literature at this time and developed hydrologic procedures for design flow estimation. Sherman had recently published his unit hydrograph theory in 1932, and later in 1938 Snyder, who had been charged by the Water Resource Council to develop a synthetic unit hydrograph, published his famous paper. The SCS unit hydrograph theory was developed by Victor Mockus in the late 1950s. Most if not all of the theories at that time reported the rainfall‐runoff process for floods as a surface phenomenon, and as such those theories all required some type of a timing parameter to estimate watershed response time. This article documents the development of the SCS lag equation.     

Evaluating livestock system environmental performance with whole-farm nutrient balance

As a part of the USEPA's concentrated animal feeding operation (CAFO) final rule, all CAFOs are required to develop and implement a nutrient management plan (NMP). The USEPA's emphasis on better management of nutrients appropriately targets a critical environmental issue associated with animal production. The concentration of animals in livestock feeding operations, often separate from feed grain production, requires importing of substantial quantities of feed nutrients. Due to the inefficiencies of nutrient utilization in livestock production, quantities of nitrogen (N) and phosphorus (P) in manure greater than can be utilized in local crop production often result. With the focus of the USEPA's NMP rules on internal farm manure management planning, nutrient concentrations resulting from animal concentration may not be adequately addressed by compliance with the USEPA rules alone. A review of two mandatory and two voluntary nutrient management strategies is made by comparing whole-farm nutrient balance for a case-study beef cattle feedlot. The results suggest that voluntary BMPs, such as modification to animal feeding program and exporting of manure, can have greater environmental benefits (30-60% reduction in P accumulation for case-study farm) than mandatory NMPs and buffers (5-7% reduction in P accumulation for case-study farm) for a typical beef cattle feedlot. Whole-farm nutrient balance procedures can also be valuable for reviewing the nutrient performance of livestock systems.