Ironing Out Genes in the Environment: An Experimental Study of the DNA-Goethite Interface.

DNA fate in soil plays an important role in the cycling of genetic information in the environment. Adsorption onto mineral surfaces has great impact on this function. This study probes the kinetics, equilibrium behavior and bonding mechanisms associated with adsorption of DNA onto goethite, a common soil mineral. Surface sensitive ATR-FTIR and XPS approaches are applied to directly characterize the DNA-goethite interface. Adsorption kinetics follow a pseudo-first-order model, suggesting adsorption rate is surface limited. Adsorption rate constants increase with DNA concentration, ranging from 3.29 × 10-3 to 3.55 × 10-1 min-1. Equilibrium adsorption, as monitored by ATR-FTIR and XPS, follows the Langmuir model, with a high affinity of DNA for goethite observed (K = 1.25 × 103 and 9.48 × 102 mL/mg for ATR-FTIR and XPS, respectively). ATR-FTIR and XPS characterization of the structure of surface adsorbed DNA demonstrates inner-sphere coordination between backbone phosphate groups of DNA and goethite. Furthermore, adsorbed DNA retains a B-form, suggesting the DNA helix adsorbs on goethite without degradation or alteration to helical structure, despite binding of backbone phosphate groups. This work advances our understanding of the environmental behavior of DNA by characterizing the mechanism of adsorption onto a prominent soil mineral.

Microscale Investigations of Soil Heterogeneity: Impacts on Zinc Retention and Uptake in Zinc-Contaminated Soils.

Metal contaminants in soils can persist for millennia, causing lasting negative impacts on local ecosystems. Long-term contaminant bioavailability is related to soil pH and to the strength and stability of solid-phase associations. We combined physical density separation with synchrotron-based microspectroscopy to reduce solid-phase complexity and to study Zn speciation in field-contaminated soils. We also investigated Zn uptake in two Zn-hyperaccumulating ecotypes of (Ganges and Prayon). Soils were either moderately contaminated (500-800 mg Zn kg via contaminated biosolids application) or grossly enriched (26,000 mg Zn kg via geogenic enrichment). Soils were separated using sodium polytungstate into three fractions: light fraction (LF) (<1.6 g cm), medium fraction (MF) (1.6-2.8 g cm), and heavy fraction (HF) (>2.8 g cm). Approximately 45% of the total Zn was associated with MF in biosolids-contaminated soils. From these data, we infer redistribution to the MF after biosolids application because Zn in biosolids is principally associated with HF and LF. Our results suggest that increasing proportions of HF-associated Zn in soils may be related to greater relative Zn removal by Zn hyperaccumulating plants. Using density fractions enabled assessment of Zn speciation on a microscale despite incomplete fractionation. Analyzing both density fractions and whole soils revealed certain phases (e.g., ZnS, Zn coprecipitated with Fe oxides) that were not obvious in all analyses, indicating multiple views of the same soils enable a more complete understanding of Zn speciation.

Soil geochemical factors regulate Cd accumulation by metal hyperaccumulating Noccaea caerulescens (J. Presl & C. Presl) F.K. Mey in field-contaminated soils.

Cadmium contamination in soil is a substantial global problem, and of significant concern due to high food-chain transfer. Cadmium hyperaccumulators are of particular interest because of their ability to tolerate and take up significant amounts of heavy metal pollution from soils. One particular plant, Noccaea caerulescens (formerly, Thlaspi caerulescens), has been extensively studied in terms of its capacity to accumulate heavy metals (specifically Zn and Cd), though these studies have primarily utilized hydroponic and metal-spiked model soil systems. We studied Cd and nutrient uptake by two N. caerulescens ecotypes, Prayon (Zn-only hyperaccumulator) and Ganges (Zn- and Cd-hyperaccumulator) in four long-term field-contaminated soils. Our data suggest that individual soil properties such as total soil Cd, Zn:Cd molar ratio, or soil pH do not accurately predict Cd uptake by hyperaccumulating plants. Additionally, total Cd uptake by the hyperaccumulating Ganges ecotype was substantially less than its physiological capacity, which is likely due to Cd-containing solid phases (primarily iron oxides) and pH that play an important role in regulating and limiting Cd solubility. Increased P accumulation in the Ganges leaves, and greater plant Fe accumulation from Cd-containing soils suggests that rhizosphere alterations via proton, and potentially organic acid, secretion may also play a role in nutrient and Cd acquisition by the plant roots. The current study highlights the role that soil geochemical factors play in influencing Cd uptake by hyperaccumulating plants. While these plants may have high physiological potential to accumulate metals from contaminated soils, individual soil geochemical factors and the plant-soil interactions in that soil will dictate the actual amount of phytoextractable metal. This underlines the need for site-specific understanding of metal-containing solid phases and geochemical properties of soils before undertaking phytoextraction efforts.

Reduction of silver solubility by humic acid and thiol ligands during acanthite (beta-Ag2S) dissolution.

Precipitation of highly insoluble metal sulfide minerals like acanthite (beta-Ag2S) or red cinnabar (HgS) is in principle an effective means to reduce metal availability and toxicity in contaminated soils. Unfortunately, experiments have shown that red cinnabar may be solubilized in the presence of dissolved organic matter or thiol ligands. To determine whether the same applies to acanthite, a laboratory synthesized beta-Ag2S mineral was incubated for up to 3 weeks in the presence of KNO3, dissolved humic acids, cysteine, methionine and thiosulfate. XPS analysis identified Ag2O (52%), Ag2SO4 (8%) and Ag2S (40%) on the particle surfaces. Ag was released into solution in the presence of KNO3 and methionine, presumably from mixed-oxidation surface layers. Contrary to earlier results with cinnabar, however, humic acids reduced Ag concentrations in solution by about 75%, and cysteine and thiosulfate, each containing a free -SH functional group, almost completely suppressed Ag release into solution.