Passive remediation of coalbed natural gas co-produced water using zeolite.

Coalbed natural gas (CBNG) co-produced waters can contain sodium (Na(+)) concentrations that may be environmentally detrimental if discharged to receiving bodies of water or applied to land surfaces. A field demonstration and companion laboratory studies were conducted to evaluate the use of a Bear River zeolite (BR-zeolite) for mitigating impacts associated with Na(+) in CBNG waters. Bench-scale kinetic and adsorption isotherm studies were performed to determine both the rate and extent of sodium Na(+) adsorption and assess the effects of bicarbonate (HCO3(-)) and chloride (Cl(-)) anions. Results of these studies showed that the adsorption of Na(+) on BR-zeolite followed the Langmuir adsorption model with maximum adsorption equal to 21 and 18 g Na(+)/kg zeolite with 0.0012 and 0.0006 L/mg Langmuir coefficients (KL) for sodium bicarbonate and sodium chloride, respectively. The kinetics study indicated that the sorption of Na(+) was inversely related to the size of the zeolite particles with significantly greater adsorption for smaller particles. The field demonstration evaluated the effectiveness of BR-zeolite for mitigating infiltration losses from Na(+) in CBNG waters. The field site utilized 12 open boreholes, each installed to a depth of approximately 1.8 m. Each borehole was lined with a 3.0 m long, 15 cm diameter schedule 40 PVC pipe and fitted with an automatic data logging pressure transducer for measuring water levels over time. The BR-zeolite was found to mitigate much of the deleterious effect that high sodium adsorption ratio (SAR = 27 (mol/m(3))(1/2)) CBNG co-produced water had on soil permeabilities.

Improving saline-sodic coalbed natural gas water quality using natural zeolites.

Management of saline-sodic water from the coalbed natural gas (CBNG) industry in the Powder River Basin (PRB) of Wyoming and Montana is a major environmental challenge. Clinoptilolie zeolites mined in Nevada, California, and New Mexico were evaluated for their potential to remove sodium (Na+) from CBNG waters. Based on the exchangeable cation composition, naturally occurring calcium (Ca2+)-rich zeolites from New Mexico were selected for further evaluation. Batch adsorption experiments were conducted to evaluate the potential of the Ca(2+)-rich natural clinoptilolites to remove Na+ from saline-sodic CBNG waters. Batch adsorption experiments indicated that Na+ adsorption capacity ofclinoptilolite ranged from 4.3 (4 x 6 mesh) to 7.98 g kg(-1) (14 x 40 mesh). Among the different adsorption isotherms investigated, the Freundlich Model fitted the data best for smaller-sized (6 x 8, 6 x 14, and 14 x 40 mesh) zeolites. Passing the CBNG water through Ca(2+)-rich zeolite columns reduced the salt content (electrical conductivity [EC]) by 72% with a concurrent reduction in sodium adsorption 10 mmol 1/2 L(-1/2). Zeolite technology appears to be an effective water treatment alternative to industrial membrane treatment for removing Na+ from poor-quality CBNG waters.

Salinity and sodicity of weathered minesoils in northwestern new Mexico and northeastern Arizona.

Evolving relationships between electrical conductivity (EC) and sodium adsorption ratio (SAR) in reconstructed soils at surface mines have been insufficiently documented in the literature. Some minesoils (i.e., rootzone material) are classified as saline, sodic, or saline-sodic and are considered unsuitable for revegetation. Weatherable minerals such as calcite and gypsum are common in alkaline minesoils and on dissolution tend to mitigate elevated SAR levels by maintaining or increasing electrolytes in the soil and providing sources of exchangeable calcium and magnesium. Topsoils (i.e., coversoils) contribute to mitigation of sodic conditions when soluble cations are translocated from coversoils into the underlying minesoils. This study evaluated the weathering characteristics of minesoils sites from three surface coal mines in northwestern New Mexico and northeastern Arizona. Minesoils were grouped into 11 classes based on EC and SAR. After 6 to 14 yr, differences between upper and lower halves of the coversoils suggest general increases occurred with EC, SAR, chloride (Cl(-)), and sulfate (SO(4)(2-)) with depth. Within the reclaimed minesoils, there were several significant (P < 0.05 or < 0.10) relationships among EC and SAR that related to Minesoil Class. Lower SAR levels with corresponding increases in EC compared to baseline minesoils were more apparent in upper minesoil depths (0-5 and 5-15 cm). Minesoil anion concentrations suggested coversoil leachates and gypsum dissolution influenced EC and SAR chemistry. Over time, chemical changes have increased the apparent stability of the saline and sodic reclaimed minesoils studied thereby reducing risks associated with potential aggregate slaking and clay particle dispersion.

Soil and plant responses from land application of saline-sodic waters: implications of management.

Land application of co-produced waters from coalbed natural gas (CBNG) wells is one management option used in the Powder River Basin (PRB) of Wyoming and Montana. Unfortunately, the co-produced CBNG waters may be saline and/or sodic. The objective of this study was to examine the effects of irrigation with CBNG waters on soils and plants in the PRB. Soil properties and vegetation responses resulting from 1 to 4 yr of saline-sodic water (electrical conductivity [EC], 1.6-4.8 dS m(-1); sodium adsorption ratio [SAR], 17-57 mmol(1/2) L(-1/2)) applications were studied during 2003 and 2004 field seasons on sites (Ustic Torriorthent, Haplocambid, Haplargid, and Paleargid) representing native range grasslands, seeded grass hayfields, and alfalfa hayfields. Parameters measured from each irrigated site were compared directly with representative non-irrigated sites. Soil chemical and physical parameters, including pH, EC, SAR, exchangeable sodium percent, texture, bulk density, infiltration, and Darcy flux rates, were measured at various depth intervals to 120 cm. Multiple-year applications of saline-sodic water produced consistent trends of increased soil EC and SAR values to depths of 30 cm, reduced surface infiltration rates, and lowered Darcy flux rates to 120 cm. Significant differences (p < or = 0.05) were determined between irrigated and non-irrigated areas for EC, SAR, infiltration rates, and Darcy flux (p < or = 0.10) at most sites. Saline-sodic CBNG water applications significantly increased native perennial grass biomass production and cover on irrigated as compared with non-irrigated sites; however, overall species evenness decreased. Biological effects were variable and complex, reflecting site-specific conditions and water and soil management strategies.

Cumulative soil chemistry changes from land application of saline-sodic waters.

Management of large volumes (60,000 ha-m) of co-production water associated with coal bed natural gas (CBNG) water extraction is a potential concern in the Powder River Basin (PRB) of Wyoming and Montana due to elevated water salinity and sodicity levels. Land application of saline-sodic CBNG water is a common water management method being practiced in the PRB, which can result in deterioration in soil quality. The objective of this study was to evaluate effects from 1 to 4 yr of land application with CBNG water on soil chemical properties at six study sites (fine to loamy, mixed to smectitic, mesic, Ustic Ardisols and Entisols) in the Wyoming PRB region. Changes in chemistry of soils collected from six depths irrigated with CBNG water were compared with representative nonirrigated soils. Applications of CBNG water significantly increased soil EC, SAR, and ESP values (up to 21, 74, and 24 times, respectively) compared with nonirrigated soils. Differences in soil chemical properties between an irrigated and nonirrigated coarse-textured soil were less than that of fine-textured soils, emphasizing texture as an important factor for salinity buildup. Pretreatment of CBNG water using a sulfur burner and application of gypsum and elemental S soil amendments reduced soil pH but did not prevent the build-up of salts and sodium. Study results suggest that current CBNG water management strategies are not as effective as projected. Additional research is needed to develop management strategies appropriate for mitigating adverse effects of CBNG water irrigation.

Soil chemical changes resulting from irrigation with water co-produced with coalbed natural gas.

Land application of coalbed natural gas (CBNG) co-produced water is a popular management option within northwestern Powder River Basin (PRB) of Wyoming. This study evaluated the impacts of land application of CBNG waters on soil chemical properties at five sites. Soil samples were collected from different depths (0-5, 5-15, 15-30, 30-60, 60-90, and 90-120 cm) from sites that were irrigated with CBNG water for 2 to 3 yr and control sites. Chemical properties of CBNG water used for irrigation on the study sites indicate that electrical conductivity of CBNG water (EC(w)) and sodium adsorption ratio of CBNG water (SAR(w)) values were greater than those recommended for irrigation use on the soils at the study sites. Soil chemical analyses indicated that electrical conductivity of soil saturated paste extracts (EC(e)) and sodium adsorption ratio of soil saturated paste extracts (SAR(e)) values for irrigated sites were significantly greater (P < 0.05) than control plots in the upper 30-cm soil depths. Mass balance calculations suggested that there has been significant buildup of Na in irrigated soils due to CBNG irrigation water as well as Na mobilization within the soil profiles. Results indicate that irrigation with CBNG water significantly impacts certain soil properties, particularly if amendments are not properly utilized. This study provides information for better understanding changes in soil properties due to land application of CBNG water. These changes must be considered in developing possible criteria for preserving fragile PRB ecosystems.

Sorption of MS2 bacteriophage to layered double hydroxides: effects of reaction time, pH, and competing anions.

Batch sorption and column breakthrough studies were conducted to investigate the potential of layered double hydroxides (LDHs) to remove bacteriophage MS2 from contaminated waters. All four of the LDHs evaluated in this study had very high retention capacities for MS2. Sorption results showed that MS2 could be completely removed from 5.2 x 10(2) plaque-forming units (pfu)/mL solution by Mg-Al LDH 2 (i.e., 2:1 Mg to Al ratio LDH), with the highest sorption capacity observed in this study of 1.51 x 10(10) pfu/g. Attachment of MS2 to LDHs was a rapid process and reached quasi-equilibrium after a 1-h reaction time. Within the pH range studied (pH 4-9), Mg-Al LDH 2 showed high sorption potential for MS2 at all pH values but sorption decreased slightly with increasing solution pH. Background solution anions influenced virus sorption, with SO4(2-) and HPO4(2-) decreasing sorption significantly whereas the presence of NO3- had little effect on the attachment of MS2 to Mg-Al LDH 2. The addition of another virus (phiX174) only caused a slight decrease in the retention of MS2 by Mg-Al LDH 2, suggesting that there was insignificant competitive sorption between MS2 and phiX174 on LDH surfaces. Results from column experiments indicate that there was no MS2 breakthrough from columns packed with Mg-Al LDH 2-coated sand, suggesting complete MS2 retention at the virus concentration tested. The high mass recovery by beef extract solution revealed that the removal of viruses by the LDH was due to sorption of MS2 to LDH surfaces, rather than inactivation.

Soil and plant selenium at a reclaimed uranium mine.

Selenium (Se) associated with reclaimed uranium (U) mine lands may result in increased food chain transfer and water contamination. To assess post-reclamation bioavailability of Se at a U mine site in southeastern Wyoming, we studied soil Se distribution, dissolution, speciation, and sorption characteristics and plant Se accumulation. Phosphate-extractable soil Se exceeded the critical limit of 0.5 mg/kg in all the samples, whereas total soil Se ranged from a low (0.6 mg/kg) to an extremely high (26 mg/kg) value. Selenite was the dominant species in phosphate and ammonium bicarbonate-diethylenetriamine pentaacetic acid (AB-DTPA) extracts, whereas selenate was the major Se species in hot water extracts. Extractable soil Se concentrations were in the order of KH2PO4 > AB-DTPA > hot water > saturated paste. The soils were undersaturated with respect to various Se solid phases, albeit with high levels of extractable Se surpassing the critical limit. Calcium and Mg minerals were the potential primary solids controlling Se dissolution, with dissolved organic carbon in the equilibrium solutions resulting in enhanced Se availability. Adsorption was a significant (r2 = 0.76-0.99 at P < 0.05) mechanism governing Se availability and was best described by the initial mass isotherm model, which predicted a maximum reserve Se pool corresponding to 87% of the phosphate-extractable Se concentrations. Grasses, forbs, and shrubs accumulated 11 to 1800 mg Se/kg dry weight. While elevated levels of bioavailable Se may be potentially toxic, the plants accumulating high Se may be used for phytoremediation, or the palatable forage species may be used as animal feed supplements in Se-deficient areas.

Assessment of the Fate of Two Herbicides in a Wyoming Rangeland Soil: Column Studies.

Extensive use of dicamba (2-methoxy-3,6-dichlorobenzoic acid) and picloram (4-amino-3,5,6-trichloropicolinic acid) in arid Wyoming, along with large volumes of irrigation water used in some areas, has created a concern for the potential contamination of surface and groundwaters by these herbicides. Persistence and mobility of dicamba and picloram were investigated in a Wyoming rangeland soil using batch adsorption and soil column studies. The objectives of this study were to characterize soil chemical and physical properties that affect herbicide transport, examine herbicide sorption, model herbicide movement, and estimate degradation rate constants. Essentially no sorption of dicamba was detected; however, picloram sorption was greatest in the highest organic C content horizon. Both saturated (5.90, 2.96, and 0.82 kg ha-1 dicamba and 1.85, 0.97, and 0.47 kg ha-1 picloram) and unsaturated (2.76 and 1.00 kg ha-1 for dicamba and picloram, respectively) column experiments were conducted. The herbicides and Br tracer (34, 38, 69, and 137 mg L-1 ) were displaced through the soil columns using distilled water that was added in daily increments (60 mL d-1 ). Degradation rate constants were calculated using both a simple recovery fraction technique and by matching LEACHP-generated breakthrough curves to experimental data. For the two columns receiving intermediate application rates, anaerobic picloram dissipation was more rapid (t1/2 = 19 d) than for aerobic conditions (t1/2 = 87 d). The rate of dissipation of dicamha was approximately the same under aerobic and anaerobic conditions (t1/2 = 15 and 17 d in the saturated and unsaturated columns, respectively). Piclorum and dicamba dissipation was more rapid at the lowest application rates, with t1/2 of 13 and 10 d. At the highest application rates, t1/2 of 23 and 17 d were measured for picloram and dicamba, respectively. Both herbicides were found to be highly mobile, with the mobility of picloram increasing at higher pore-water velocities.