Corrections for measurements of tritium in subterranean vapor using silica gel

Hazardous contaminants buried within vadose zones can accumulate in soil gas. The concentrations and spatial extent of these contaminants are measured to evaluate potential transport to groundwater for public risk evaluation. Tritium is an important contaminant found and monitored for in vadose zones across numerous sites within the US nuclear weapons complex, including Los Alamos National Laboratory. The extraction, collection, and laboratory analysis of tritium from subterranean soil gas presents numerous technical challenges that have not been fully studied. Particularly, the lack of moisture in the soil gas in the vadose zone makes it difficult to obtain enough sample (e.g., >5 g) to provide for the required measurement sensitivity, and often, only small amounts of moisture can be collected. Further, although silica gel has high affinity for water vapor and is prebaked prior to sampling, there is still sufficient residual moisture in the prebaked gel to dilute the relatively small amount of sampled moisture; thereby, significantly lowering the ??true?? tritium concentration in the soil gas. This paper provides an evaluation of the magnitude of the bias from dilution, provides methods to correct past measurements by applying a correction factor (CF), and evaluates the uncertainty of the CF values. For this, 10,000 Monte Carlo calculations were performed, and distribution parameters of CF values were determined and evaluated. The mean and standard deviation of the distribution of CF values were 1.53 ± 0.36, and the minimum, median, and maximum values were 1.14, 1.43, and 5.27, respectively.     

Stimulation of reductive dechlorination of hexachlorobenzene in soil by inducing the native microbial activity

The reductive dechlorination and behaviour of ¹⁴C-hexachlorobenzene (HCB) was investigated in an arable soil. The activity of the native anaerobic microbial communities could be induced by saturating the soil with water. Under these conditions high rates of dechlorination were observed. After 20 weeks of incubation only 1% of the applied ¹⁴C-HCB could be detected in the fraction of extractable residues. Additional organic substances, like wheat straw and lucerne straw, however considerably delayed and reduced the dechlorination process in the soil. The decline of HCB was not only caused by dechlorination but also by the formation of non-extractable residues, whereby their amounts varied with time depending on the experimental conditions. Several dechlorination products were detected, indicating the following main HCB transformation pathway: HCB → PCB → 1,2,3,5-TeCB → 1,3,5-TCB → 1,3-DCB, with 1,3,5-TCB as main intermediate dechlorination product. The other TeCB-, TCB- and DCB-isomers were also detected in low amounts, showing the presence of more than one dechlorination pathway. Since the methane production rates were lowest when the dechlorination rates were highest, it can be assumed that methanogenic bacteria were not involved in the dechlorination process of HCB. The established ¹⁴C-mass balances show, that with increasing dechlorination and incubation times, the ¹⁴C-recoveries decreased.     

Reactivity of the plant growth regulator paclobutrazol (cultar) with two tropical soils of the northeast semiarid region of Brazil

The reactivity of paclobutrazol (PBZ, a plant growth retardant) with a Yellow Ultisol and a Vertisol from the semiarid northeast region of Brazil was evaluated through batch sorption experiments and modeling. Although not instantaneous, the sorption kinetic of PBZ (pure and formulated) was fast (a few hours) in both soils. The sorption kinetics were well described by a second-order (dS(t)/dt=k(2)(S(e2)-S(t))(2)) but not by a first-order model. The sorption isotherms were found to be linear and the calculated K(D) values were 8.8 +/- 0.11 and 7.4 +/- 0.2 L kg(-1) for pure PBZ in the Ultisol and the Vertisol, respectively. The corresponding K(OC) values were 1275 +/- 34 (logK(OC) = 3.11) and 1156 +/- 49 (logK(OC) = 3.06) L kg(-1), respectively. Considering the very different texture of the two soils and the similar K(OC) values determined, these results showed that in both soils, the sorption of PBZ is dominantly controlled by organic matter, although some interactions of PBZ with iron oxides (goethite) were observed in the Ultisol. Based on these sorption parameters a low leachability potential of PBZ in soils is anticipated, as they correspond to a groundwater ubiquity score (GUS) ranging from 2.0 to 2.7, i.e., moderately to not mobile, in contradiction with the actual groundwater situation in Brazil. This work stresses the need to evaluate and predict the risk associated with aquifer contamination by this widely used plant growth regulator.     

Soil-to-root transfer and translocation of polycyclic aromatic hydrocarbons by vegetables grown on industrial contaminated soils

Polycyclic aromatic hydrocarbons (PAHs) are possible contaminants in some former industrial sites, representing a potential risk to human health if these sites are converted to residential areas. This work was conducted to determine whether PAHs present in contaminated soils are transferred to edible parts of selected vegetables. Soils were sampled from a former gasworks and a private garden, exhibiting a range of PAH concentrations (4 to 53 to 172 to 1263 and 2526 mg PAHs kg-1 of dry soil), and pot experiments were conducted in a greenhouse with lettuce (Lactuca sativa L. var. Reine de Mai), potato (Solanum tuberosum L. var. Belle de Fontenay), and carrot (Daucus carota L. var. Nantaise). At harvest, above- and below ground biomass were determined and the PAH concentrations in soil were measured. In parallel, plates were placed in the greenhouse to estimate the average PAH-dust deposition. Results showed that the presence of PAHs in soils had no detrimental effect on plant growth. Polycyclic aromatic hydrocarbons were detected in all plants grown in contaminated soils. However, their concentration was low compared with the initial soil concentration, and the bioconcentration factors were low (i.e., ranging from 13.4 x 10(-4) in potato and carrot pulp to 2 x 10(-2) in potato and carrot leaves). Except in peeled potatoes, the PAH concentration in vegetables increased with the PAH concentration in soils. The PAH distribution profiles in plant tissues and in soils suggested that root uptake was the main pathway for high molecular weight PAHs. On the opposite, lower molecular weight PAHs were probably taken up from the atmosphere through the leaves as well as by roots.