Pressure-controlled injection of guar gum stabilized microscale zerovalent iron for groundwater remediation.

The paper reports a pilot injection test of microsized zerovalent iron (mZVI) dispersed in a guar gum shear thinning solution. The test was performed in the framework of the EU research project AQUAREHAB in a site in Belgium contaminated by chlorinated aliphatic hydrocarbons (CAHs). The field application was aimed to overcome those critical aspects which hinder mZVI field injection, mainly due to the colloidal instability of ZVI-based suspensions. The iron slurry properties (iron particles size and concentration, polymeric stabilizer type and concentration, slurry viscosity) were designed in the laboratory based on several tests (reactivity tests towards contaminants, sedimentation tests and rheological measurements). The particles were delivered into the aquifer through an injection well specifically designed for controlled-pressure delivery (approximately 10 bars). The well characteristics and the critical pressure of the aquifer (i.e. the injection pressure above which fracturing occurs) were assessed via two innovative injection step rate tests, one performed with water and the other one with guar gum. Based on laboratory and field preliminary tests, a flow regime at the threshold between permeation and preferential flow was selected for mZVI delivery, as a compromise between the desired homogeneous distribution of the mZVI around the injection point (ensured by permeation flow) and the fast and effective injection of the slurry (guaranteed by high discharge rates and injection pressure, resulting in the generation of preferential flow paths). A monitoring setup was designed and installed for the real-time monitoring of relevant parameters during injection, and for a fast determination of the spatial mZVI distribution after injection via non-invasive magnetic susceptibility measurements.

In-situ zinc bioprecipitation by organic substrate injection in a high-flow, poorly reduced aquifer.

We investigated if in-situ metal bioprecipitation (ISMP) is applicable to remediate a highly permeable zinc-contaminated aquifer at a metal-processing factory in Maasmechelen, Belgium. A large (more than 200m long and 70m wide) groundwater contamination plume has developed, with zinc concentrations in the range of 1-100mg/L, whereas the legal Flemish clean-up standard is 0.5mg/L. The estimated groundwater flow velocity is in the range 0.2-1m/d. The groundwater is relatively oxidized, naturally low in DOC (<1mg/L) and relatively low in sulfate (40-50mg/L). We conducted both laboratory feasibility tests as well as a long-term field pilot test in two sections of the plume. In the laboratory microcosm tests, zinc bioprecipitation (following addition of organic substrate and sulfate) removed more than 99% of the zinc from the water phase. Lactate, glycerol and vegetable oil were equally effective as substrates. 28-day anaerobic leaching tests indicated that the metal precipitates that were formed are stable, but they also suggested that substrate addition increases the solubility (leachability) of arsenic and manganese. In the field test, Zn concentrations were reduced by 2 to 3 orders of magnitude within the 232 day testing period and stayed low for the following 6 months in both pilot zones. In the field, no mobilization of arsenic occurred but manganese groundwater concentrations increased from 0.01-0.6mg/L to 0.4-6.5mg/L. Dissolved iron concentrations also increased markedly from below detection limits to concentrations as high as 67mg/L. Zinc concentrations in groundwater were closely correlated to pH and redox potential (Eh): plotting y=[Zn] against x=pH/log(Eh), an exponential relationship was found:

Reduction of cyclopropene by NifV- and wild-type nitrogenases from Klebsiella pneumoniae.

The nitrogenase from wild-type Klebsiella pneumoniae reduces cyclopropene to cyclopropane and propene in the ratio 1:2 at pH 7.5. We show in this paper that the nitrogenase from a nifV mutant of K. pneumoniae also reduces cyclopropene to cyclopropane and propene, but the ratio of products is now 1:1.4. However, both nitrogenases exhibit the same Km for cyclopropene (2.1 x 10(4) +/- 0.2 x 10(4) Pa), considerably more than the Km for the analogous reaction with Azotobacter vinelandii nitrogenase under the same conditions (5.1 x 10(3) Pa). Analysis of the data shows that the different product ratio arises from the slower production of propene compared with cyclopropane by the mutant nitrogenase. During turnover, both nitrogenases use a large proportion of the electron flux for H2 production. CO inhibits the reduction of cyclopropene by both K. pneumoniae proteins, but the mutant nitrogenase exhibits 50% inhibition at approx. 10 Pa, whereas the corresponding value for the wild-type nitrogenase is approx. 110 Pa. However, H2 evolution by the mutant enzyme is much less affected than is cyclopropene reduction. CO inhibition of cyclopropene reduction by the nitrogenases coincides with a relative increase in H2 evolution, so that in the wild-type (but not the mutant) the electron flux is approximately maintained. The cyclopropane/propene production ratios are little affected by the presence of CO within the pressure ranges studied at least up to 50% inhibition.