Controls on Nitrous Oxide Emissions from the Hyporheic Zones of Streams.

The magnitude and mechanisms of nitrous oxide (N2O) release from rivers and streams are actively debated. The complex interactions of hydrodynamic and biogeochemical controls on emissions of this important greenhouse gas preclude prediction of when and where N2O emissions will be significant. We present observations from column and large-scale flume experiments supporting an integrative model of N2O emissions from stream sediments. Our results show a distinct, replicable, pattern of nitrous oxide generation and consumption dictated by subsurface (hyporheic) residence times and biological nitrogen reduction rates. Within this model, N2O emission from stream sediments requires subsurface residence times (and microbially mediated reduction rates) be sufficiently long (and fast reacting) to produce N2O by nitrate reduction but also sufficiently short (or slow reacting) to limit N2O conversion to dinitrogen gas. Most subsurface exchange will not result in N2O emissions; only specific, intermediate, residence times (reaction rates) will both produce and release N2O to the stream. We also confirm previous observations that elevated nitrate and declining organic carbon reactivity increase N2O production, highlighting the importance of associated reaction rates in controlling N2O accumulation. Combined, these observations help constrain when N2O release will occur, providing a predictive link between stream geomorphology, hydrodynamics, and N2O emissions.

Aquifer Arsenic Cycling Induced by Seasonal Hydrologic Changes within the Yangtze River Basin.

Consumption of groundwater containing >10 µg L(-1) arsenic (As) adversely impacts more than 100 million people worldwide. Multiyear trends in aquifer As concentrations have been documented, but strong seasonal variations are not commonly observed. Here we report dramatic seasonal changes in As concentrations and aquifer chemistry within the Jianghan Plain of the Yangtze River, China. At some wells, concentrations fluctuate by more than an order of magnitude within a single year (100-1200 µg L(-1)). Groundwater extraction and sustained water levels of surface channels during the dry season induces a strong downward hydraulic gradient, seasonally supplying oxidizing (oxygen, nitrate) water to the otherwise anoxic aquifer. Oxygen and/or nitrate addition promotes a transient drop in As concentrations for 1-3 months. When recharge ceases, reducing, low-arsenic conditions are reestablished by reactive, endogenous organic carbon. Temporal variability in As concentrations is especially problematic because it increases the probability of false-negative well testing during low-arsenic seasons. However, periods of low As may also provide a source of less toxic water for irrigation or other uses. Our results highlight the vulnerability and variability of groundwater resources in the Jianghan Plain and other inland basins within Asia to changing geochemical conditions, both natural and anthropogenic, and reinforce that continued monitoring of wells in high-risk regions is essential.

Near-surface wetland sediments as a source of arsenic release to ground water in Asia.

Tens of millions of people in south and southeast Asia routinely consume ground water that has unsafe arsenic levels. Arsenic is naturally derived from eroded Himalayan sediments, and is believed to enter solution following reductive release from solid phases under anaerobic conditions. However, the processes governing aqueous concentrations and locations of arsenic release to pore water remain unresolved, limiting our ability to predict arsenic concentrations spatially (between wells) and temporally (future concentrations) and to assess the impact of human activities on the arsenic problem. This uncertainty is partly attributed to a poor understanding of groundwater flow paths altered by extensive irrigation pumping in the Ganges-Brahmaputra delta, where most research has focused. Here, using hydrologic and (bio)geochemical measurements, we show that on the minimally disturbed Mekong delta of Cambodia, arsenic is released from near-surface, river-derived sediments and transported, on a centennial timescale, through the underlying aquifer back to the river. Owing to similarities in geologic deposition, aquifer source rock and regional hydrologic gradients, our results represent a model for understanding pre-disturbance conditions for other major deltas in Asia. Furthermore, the observation of strong hydrologic influence on arsenic behaviour indicates that release and transport of arsenic are sensitive to continuing and impending anthropogenic disturbances. In particular, groundwater pumping for irrigation, changes in agricultural practices, sediment excavation, levee construction and upstream dam installations will alter the hydraulic regime and/or arsenic source material and, by extension, influence groundwater arsenic concentrations and the future of this health problem.

A permeable reactive barrier for treatment of heavy metals.

Historical storage of ore concentrate containing sulfide minerals at an industrial site in British Columbia, Canada, has resulted in widespread contamination of the underlying soil and ground water. The oxidation of sulfide minerals has released significant quantities of heavy metals, including Cu, Cd, Co, Ni, and Zn, into the ground water. A pilot-scale, compost-based, sulfate-reducing permeable reactive barrier was installed in the path of the dissolved heavy-metal plume. The permeable reactive barrier uses sulfate-reducing bacteria to promote precipitation of heavy metals as insoluble metal sulfides. Monitoring over a 21-month period indicated significant removal of heavy metals within the barrier. Copper concentrations declined from a mean concentration of 3,630 pg/L in the influent to a mean concentration within the barrier of 10.5 microg/L, Cd from 15.3 microg/L to 0.2 microg/L, Co from 5.3 microg/L to 1.1 microg/L, Ni from 131 pg/L to 33.0 microg/L, and Zn from 2,410 microg/L to 136 pg/L. Within the lower half of the barrier where tidal influences were more limited and sulfate-reducing conditions were better maintained, mean treatment levels of 2.9 microg/L (Cu), 0.1 microg/L (Cd), 0.4 microg/L (Co), 2.7 microg/L (Ni), and 6.3 microg/L (Zn) were observed.

Competing Fe (II)-induced mineralization pathways of ferrihydrite.

Owing to its high surface area and intrinsic reactivity, ferrihydrite serves as a dominant sink for numerous metals and nutrients in surface environments and is a potentially important terminal electron acceptor for microbial respiration. Introduction of Fe (II), by reductive dissolution of Fe(III) minerals, for example, converts ferrihydrite to Fe phases varying in their retention and reducing capacity. While Fe(II) concentration is the master variable dictating secondary mineralization pathways of ferrihydrite, here we reveal thatthe kinetics of conversion and ultimate mineral assemblage are a function of competing mineralization pathways influenced by pH and stabilizing ligands. Reaction of Fe(II) with ferrihydrite results in the precipitation of goethite, lepidocrocite, and magnetite. The three phases vary in their precipitation extent, rate, and residence time, all of which are primarily a function of Fe(II) concentration and ligand type (Cl, SO4, CO3). While lepidocrocite and goethite precipitate over a large Fe(II) concentration range, magnetite accumulation is only observed at surface loadings greater than 1.0 mmol Fe(II)/g ferrihydrite (in the absence of bicarbonate). Precipitation of magnetite induces the dissolution of lepidocrocite (presence of Cl) or goethite (presence of SO4), allowing for Fe(III)-dependent crystal growth. The rate of magnetite precipitation is a function of the relative proportions of goethite to lepidocrocite; the lower solubility of the former Fe (hydr)oxide slows magnetite precipitation. A one unit pH deviation from 7, however, either impedes (pH 6) or enhances (pH 8) magnetite precipitation. In the absence of magnetite nucleation, lepidocrocite and goethite continue to precipitate at the expense of ferrihydrite with near complete conversion within hours, the relative proportions of the two hydroxides dependent upon the ligand present. Goethite also continues to precipitate at the expense of lepidocrocite in the absence of chloride. In fact, the rate and extent of both goethite and magnetite precipitation are influenced by conditions conducive to the production and stability of lepidocrocite. Thus, predicting the secondary mineralization of ferrihydrite, a process having sweeping influences on contaminant/nutrient dynamics, will need to take into consideration kinetic restraints and transient precursor phases (e.g., lepidocrocite) that influence ensuing reaction pathways.

Reductive dissolution and biomineralization of iron hydroxide under dynamic flow conditions.

Iron cycling and the associated changes in solid phase have dramatic implications for trace element mobility and bioavailability. Here we explore the formation of secondary iron phases during microbially mediated reductive dissolution of ferrihydrite-coated sand under dynamic flow conditions. An initial period (10 d) of rapid reduction, indicated by consumption of lactate and production of acetate and Fe-(II) to the pore water in association with a darkening of the column material, is followed by much lower rate of reduction to the termination of the experiment after 48 d. Although some Fe (<25%) is lost to the effluent pore water, the majority remains within the column as ferrihydrite (20-70%) and the secondary mineral phases magnetite (0-70%) and goethite (0-25%). Ferrihydrite converts to goethite in the influent end of the column where dissolved Fe(II) concentrations are low and converts to magnetite toward the effluent end where Fe(III) concentrations are elevated. A decline in the rate of Fe(II) production occurs concurrent with the formation of goethite and magnetite; at the termination of the experiment, the rate of reduction is <5% the initial rate. Despite the dramatic decrease in the rate of reduction, greater than 80% of the residual Fe remains in the ferric state. These results highlight the importance of coupled flow and water chemistry in controlling the rate and solid-phase products of iron (hydr)oxide reduction.