Effect of zero-valent iron and a redox mediator on removal of selenium in agricultural drainage water.

Effective and economical removal of selenium (Se) in agricultural drainage water is very important in Se bioremediation. Zero-valent iron (ZVI) and a redox mediator [anthraquinone-2,6-disulfonate (AQDS)] were assessed for their ability to enhance the removal of Se(VI) or Se(IV) (500 microg/L) in synthetic drainage water by Enterobacter taylorae. The results showed that E. taylorae was capable of using inexpensive sucrose to remove Se from the drainage water. During a 7-day experiment, Se(VI) was almost entirely reduced to Se(0) and transformed to organic Se in the drainage water with sucrose levels of 500 to 1000 mg/L. Addition of ZVI to the drainage water increased the removal of total soluble Se to 94.5-96.5% and limited the production of organic Se. Addition of AQDS to the drainage water with or without ZVI decreased Se(VI) removal, but enhanced the removal of Se(IV), suggesting that E. taylorae only can use anthrahydroquinone-2,6-disulfonate (AHQDS, a reduced form of AQDS) to respire Se(IV), and not Se(VI). These results show that ZVI has promising application potential in the bioremediation of Se in Se-contaminated water.

Hydrogen sulfide production and volatilization in a polymictic eutrophic saline lake, Salton Sea, California.

The Salton Sea is a large shallow saline lake located in southern California that is noted for high sulfate concentrations, substantial algal productivity, and very warm water column temperatures. These conditions are well-suited for sulfide production, and sulfide has been implicated in summer fish kills, although no studies have been conducted to specifically understand hydrogen sulfide production and volatilization there. Despite polymictic mixing patterns and relatively short accumulation periods, the amount of sulfide produced is comparable to meromictic lakes. Sulfide levels in the Salton Sea reached concentrations of 1.2 mmol L(-1) of total free sulfide in the hypolimnion and 5.6 mmol L(-1) in the sediment pore water. Strong winds in late July mixed H2S into the surface water, where it depleted the entire water column of dissolved oxygen and reached a concentration of 0.1 mmol L(-1). Sulfide concentrations exceeded the toxicity threshold of tilapia (Oreochromis mossambicus) and combined with strong anoxia throughout the water column, resulted in a massive fish kill. The mixing of sulfide into the surface waters also increased atmospheric H2S concentrations, reaching 1.0 micromol m(-3). The flux of sulfide from the sediment into the water column was estimated to range from 2-3 mmol m(-2) day(-1) during the winter and up to 8 mmol m(-2) day(-1) during the summer. Application of the two-layer model for volatilization indicates that up to 19 mmol m(-2) day(-1) volatilized from the surface during the mixing event. We estimate that as much as 3400 Mg year(-1) or approximately 26% of sulfide that diffused into the water column from the deepest sediments may have been volatilized to the atmosphere.

Application of redox mediator to accelerate selenate reduction to elemental selenium by Enterobacter taylorae.

Acceleration of bacterial reduction of selenate [Se(VI)] to insoluble elemental Se [Se(0)] plays an important role in Se bioremediation. Anthraquinone-2,6-disulfonate (AQDS), a redox mediator, was assessed for its ability to enhance the reduction of Se(VI) (2000 microg/L) to Se(0) by Enterobacter taylorae in various media. The results showed that addition of AQDS did not increase Se(VI) reduction in the media containing 50 and 250 mg/L yeast extract, suggesting that E. taylorae cannot directly use anthrahydroquinone-2,6-disulfonate (AHQDS, a reduced form of AQDS) to respire Se(VI). An increase of yeast extract concentration from 50 to 250 mg/L in the medium dramatically enhanced the AQDS function for rapid reduction of selenite [Se(IV)] to Se(0). During an 8-day experiment, 85-91% of the added Se was reduced to Se(0) in the AQDS-amended medium in comparison to formation of 46% of Se(0) in the medium without AQDS. These results show that redox mediators have great application potential in bioremediation of Se in Se-contaminated water.

Perchlorate reduction by autotrophic bacteria attached to zerovalent iron in a flow-through reactor.

Biological reduction of perchlorate by autotrophic microorganisms attached to zerovalent iron (ZVI) was studied in flow-through columns. The effects of pH, flow rate, and influent perchlorate and nitrate concentrations on perchlorate reduction were investigated. Excellent perchlorate removal performance (> or = 99%) was achieved at empty bed residence times (EBRTs) ranging from 0.3 to 63 h and an influent perchlorate concentration of 40-600 microg L(-1). At the longest liquid residence times, when the influent pH was above 7.5, a significant increase of the effluent pH was observed (pH > 10.0), which led to a decrease of perchlorate removal. Experiments at short residence times revealed that the ZVI column inoculated with local soil (Colton, CA) containing a mixed culture of denitrifiers exhibited much better performance than the columns inoculated with Dechloromonas sp. HZ for reduction of both perchlorate and nitrate. As the flow rate was varied between 2 and 50 mL min(-1), corresponding to empty bed contact times of 0.15-3.8 h, a maximum perchlorate elimination capacity of 3.0 +/- 0.7 g m(-3) h(-1) was obtained in a soil-inoculated column. At an EBRT of 0.3 h and an influent perchlorate concentration of 30 microg L(-1), breakthrough (> 6 ppb) of perchlorate in the effluent did not occur until the nitrate concentration in the influent was 1500 times (molar) greater than that of perchlorate. The mass of microorganisms attached on the solid ZVI/sand was found to be 3 orders of magnitude greater than that in the pore liquid, indicating that perchlorate was primarily reduced by bacteria attached to ZVI. Overall, the process appears to be a promising alternative for perchlorate remediation.

Controlling tailwater sediment and phosphorus concentrations with polyacrylamide in the Imperial Valley, California.

External loading of phosphorus (P) from agricultural surface discharge (tailwater) is the main cause of excessive algae growth and the eutrophication of the Salton Sea, California. Continuous polyacrylamide (PAM) applications to agricultural irrigation water inflows were evaluated as a means of reducing sediment and P in tailwater. Zero (control) and 1 mg L(-1) PAM (PAM1) treatments were compared at 17 Imperial Valley field sites. Five and 10 mg L(-1) PAM treatments (PAM5, PAM10) were conducted at one site. The particulate phosphorus (Pp) fraction was determined as the difference between total phosphorus (Pt) and the soluble phosphorus (Ps) fraction. We observed 73, 82, and 98% turbidity reduction with PAM1, PAM5, and PAM10 treatments. Although eight field sites had control tailwater sediment concentrations above the New River total maximum daily loads (TMDL), all but one were made compliant during their paired PAM1 treatments. While PAM1 and PAM10 reduced tail water Pp by 31 and 78%, none of the treatments tested reduced Ps. This may have been caused by high irrigation water Na concentrations which would reduce Ca adsorption and Ca-phosphate bridging on the PAM. The PAM1 treatments resulted in <0.5 mg L(-1) drain water polyacrylamide concentrations 1.6 km downstream of PAM addition, while PAM5 and PAM10 treatments produced > 2 mg L(-1) drain water polyacrylamide concentrations. We concluded that, although PAM practically eliminates Imperial Valley tailwater sediment loads, it does not effectively reduce tailwater Ps, the P fraction most responsible for the eutrophication of the Salton Sea.

Perchlorate reduction by autotrophic bacteria in the presence of zero-valent iron.

A series of batch experiments were performed to study the combination of zero-valent iron (ZVI) with perchlorate-reducing microorganisms (PRMs) to remove perchlorate from groundwater. In this method, H2 produced during the process of iron corrosion by water is used by PRMs as an electron donor to reduce perchlorate to chloride. Perchlorate degradation rates followed Monod kinetics, with a normalized maximum utilization rate (rmax) of 9200 microg g(-1) (dry wt) h(-1) and a half-velocity constant (Ks) of 8900 microg L(-1). The overall rate of perchlorate reduction was affected by the biomass density within the system. An increase in the OD600 from 0.025 to 0.08 led to a corresponding 4-fold increase of perchlorate reduction rate. PRM adaptation to the local environment and initiation of perchlorate reduction was rapid under neutral pH conditions. At the initial OD600 of 0.015, perchlorate reduction followed pseudo-first-order reaction rates with constants of 0.059 and 0.033 h(-1) at initial pH 7 and 8, respectively. Once perchlorate reduction was established, the bioreductive process was insensitive to the increases of pH from near neutral to 9.0. In the presence of nitrate, perchlorate reduction rate was reduced, but not inhibited completely.

Influence of aging on phosphorus sorption to alum floc in lake water.

Alum is often added to eutrophic lakes to limit the release of phosphorus from sediments. This study quantified the effect of age and extent of crystallization on the phosphate (PO4-P) sorption capacity of alum floc. Aluminum hydroxide flocs were formed from alum addition at a dose of 25 mg/L of Al3+ to Big Bear Lake waters returned to the laboratory; flocs were then aged for 4, 20, 50, 120, and 180 days in the treated lake waters. The physical and mineralogical properties of the alum floc were characterized using surface area and thermal analyses. Phosphate sorption to the floc was evaluated using filtered lake water and NaCl/NaHCO3 solutions spiked with PO4-P concentrations ranging from 0 to 100 mg/L. The Langmuir model provided reasonable fits to data (r2 = 0.97-1.00), from which sorption constants and sorption maxima were determined. Phosphate sorption decreased with increased floc age and crystallinity and decreased surface area. Phosphate sorption maximum of the alum floc aged for 6 months was about 50% lower than freshly precipitated floc, while the binding constant, Kads, decreased approximately 65% over this same time period.

Can chemical oxidation improve the permeability of infiltration basins?

The Rapid Infiltration and Extraction (RIX) facility, a soil aquifer treatment system, began taking secondary effluent from the City of San Bernardino, California, in 1996. The gradual decrease in the hydraulic conductivity of the infiltration basins at RIX has been attributed to the accumulation of organic matter in the surface sand. Periodic tillage of the surface sand to restore the permeability has mixed this organic matter to a depth of nearly 50 cm. We hypothesized that in situ chemical oxidation of the surface sand might improve the infiltration rate and increase the time between filling and drying cycles. The effect of organic matter oxidation on sand permeability was tested in laboratory sand columns treated with sodium hypochlorite, calcium hypochorite, and ozone gas. All oxidants significantly decreased the hydraulic conductivity of the surface sand. The loss in permeability was attributed to an increase in dispersed clay plus silt-sized particles that were released as a result of oxidation. This study suggests that ex situ sand-washing operations, currently being used to clean the sand, could be improved by the addition of oxidants to the wash water.

Critical evaluation of the ability of sequential extraction procedures to quantify discrete forms of selenium in sediments and soils.

Sequential extraction procedures (SEPs) have been widely used to characterize the mobility, bioavailibility, and potential toxicity of trace elements in soils and sediments. Although oft-criticized, these methods may perform best with redox-labile elements (As, Hg, Se) for which more discrete biogeochemical phases may arise from variations in oxidation number. We critically evaluated two published SEPs for Se for their specificity and precision by applying them to four discrete components in an inert silica matrix: soluble Se(VI) (selenate), Se(IV) (selenite) adsorbed onto goethite, elemental Se, and a metal selenide (FeSe; achavalite). These were extracted both individually and in a mixed model sediment. The more selective of the two procedures was modified to further improve its selectivity (SEP 2M). Both SEP 1 and SEP 2M quantitatively recovered soluble selenate but yielded incomplete recoveries of adsorbed selenite (64% and 81%, respectively). SEP 1 utilizes 0.1 M K2S2O8 to target "organically associated" Se, but this extractant also solubilized most of the elemental (64%) and iron selenide (91%) components of the model sediment. In SEP 2M, the Na2SO3 used in step III is effective in extracting elemental Se but also extracted 17% of the Se from the iron selenide, such that the elemental fraction would be overestimated should both forms coexist. Application of SEP 2M to eight wetland sediments further suggested that the Na2SO3 in step III extracts some organically associated Se, so a NaOH extraction was inserted beforehand to yield a further modification, SEP 2OH. Results using this five-step procedure suggested that the four-step SEP 2M could overestimate elemental Se by as much as 43% due to solubilization of organic Se. Although still imperfect in its selectivity, SEP 20H may be the most suitable procedure for routine, accurate fractionation of Se in soils and sediments. However, the strong oxidant (NaOCl) used in the final step cannot distinguish between refractory organic forms of Se and pyritic Se that might form under sulfur-reducing conditions.

Soil selenium uptake and root system development in plant taxa differing in Se-accumulating capability.

• Phytoremediation of Se-contaminated soils and sediments may be more feasible if accumulating taxa are identified that can extract the more refractory forms of Se. • In a glasshouse study, the capacity of six plant genotypes to take up labile and nonlabile soil Se was evaluated by amending five high-Se soils (2-21 mg kg-1 total Se) with carrier-free 75 Se, and cropping them with Astragalus bisulcatus, Astragalus canadensis, Brassica juncea, Sporobolus airoides, and two ecotypes of Stanleya pinnata. • The biologically labile pool of soil Se (L-value) was computed from the isotopic signature of the harvested shoots, and ranged from 2 to 37% of the total soil Se. The chemically labile pool (E-value) was determined via extraction in 0.1 m KCl, and ranged from 4 to 73% of total soil Se. None of the plants tested yielded L-values that were consistently greater than the E-values, suggesting that all plants, including Se hyperaccumulators, access the same labile pools of Se. • Root-growth experiments in rhizoboxes using Se-enriched soil were also performed. Although our observations were not as striking as those made for the Zn(Cd)-accumulator Thlaspi caerulescens, the tendency for roots of some Se-accumulators to proliferate in soil where Se is present deserves further investigation.

Arsenic(III) and arsenic(V) reactions with zerovalent iron corrosion products.

Zerovalent iron (Fe0) has tremendous potential as a remediation material for removal of arsenic from groundwater and drinking water. This study investigates the speciation of arsenate (As(V)) and arsenite (As(III)) after reaction with two Fe0 materials, their iron oxide corrosion products, and several model iron oxides. A variety of analytical techniques were used to study the reaction products including HPLC-hydride generation atomic absorption spectrometry, X-ray diffraction, scanning electron microscopy-energy-dispersive X-ray analysis, and X-ray absorption spectroscopy. The products of corrosion of Fe0 include lepidocrocite (gamma-FeOOH), magnetite (Fe3O4), and/or maghemite (gamma-Fe2O3), all of which indicate Fe(II) oxidation as an intermediate step in the Fe0 corrosion process. The in-situ Fe0 corrosion reaction caused a high As(III) and As(V) uptake with both Fe0 materials studied. Under aerobic conditions, the Fe0 corrosion reaction did not cause As(V) reduction to As(III) but did cause As(III) oxidation to As(V). Oxidation of As(III) was also caused by maghemite and hematite minerals indicating that the formation of certain iron oxides during Fe0 corrosion favors the As(V) species. Water reduction and the release of OH- to solution on the surface of corroding Fe0 may also promote As(III) oxidation. Analysis of As(III) and As(V) adsorption complexes in the Fe0 corrosion products and synthetic iron oxides by extended X-ray absorption fine structure spectroscopy (EXAFS) gave predominant As-Fe interatomic distances of 3.30-3.36 A. This was attributed to inner-sphere, bidentate As(III) and As(V) complexes. The results of this study suggest that Fe0 can be used as a versatile and economical sorbent for in-situ treatment of groundwater containing As(III) and As(V).