Restoring Ecosystem Function in Degraded Urban Soil Using Biosolids, Biosolids Blend, and Compost.

Many soils at former industrial sites are degraded. The objective of this research was to determine the ability of compost, biosolids, and biosolids blends to improve soil ecosystem function with minimal potential impact to surface water. Treatments rototilled into the top 12.5 cm of soil were biosolids at 202 Mg ha; biosolids at 404 Mg ha; compost at 137 Mg ha; or a blend consisting of biosolids applied at 202 Mg ha, drinking water treatment residual, and biochar. Rainfall runoff from experimental plots was collected for 3 yr. One year after soil amendments were incorporated, a native seed mix containing grasses, legumes, and forbs was planted. Soil amendments improved soil quality and nutrient pools, established a dense and high-quality vegetative cover, and improved earthworm reproductive measures. Amendments increased soil enzymatic activities that support soil function. Biosolids treatments increased the Shannon-Weaver Diversity Index for grasses. For the forbs group, control plots had the lowest diversity index and the biosolids blend had the highest diversity index. Biosolids and compost increased the number of earthworm juveniles. In general, biosolids outperformed compost. Biosolids increased N and P in rainfall runoff more than compost before vegetation was established. Several microconstituents (i.e., pharmaceutical and personal care products) were detected in runoff water but at concentrations below the probable no-effect levels and therefore should pose little impact to the aquatic environment. Future restoration design should ensure that runoff control measures are used to control sediment loss from the restored sites at least until vegetation is established.

Nuclear magnetic resonance and diffuse-reflectance infrared Fourier transform spectroscopy of biosolids-derived biocolloidal organic matter.

We extracted the acid-soluble portion of municipal biosolids, fractionated it by both molecular weight (MW) and hydrophobicity, and used various solid-state nuclear magnetic resonance (NMR) methods and diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy to characterize the fractions. Spectroscopic characterization of the MW components of the biosolids-derived organic matter fractions revealed the presence of functionally distinct groups of compounds. Quantitative 13C NMR, CH spectral editing, and several two-dimensional NMR experiments show that the high-MW hydrophilic fraction in particular is structurally simple, consisting predominantly of N-acetylated polysaccharides, perhaps derived from bacterial peptidoglycans. In the high-MW hydrophobic fraction, aromatic compounds were present in addition to the N-acetylated polysaccharides. Infrared spectroscopy confirmed that hydrophilic fractions were dominated by carbohydrates and indicated that the lower-MW fractions lacked amide moieties. Complementary interpretations of the DRIFT and NMR spectra improved our knowledge of the components separated by this fractionation scheme, allowing better characterization of biosolids organic matter. Moreover, fractionation based on both MW and hydrophobicity may prove useful in detailed characterization of the structure of biosolids-derived organic matter and other similarly heterogeneous natural organic matter in soils and sediments.

Correlation of poly(methylene)-rich amorphous aliphatic domains in humic substances with sorption of a nonpolar organic contaminant phenanthrene.

The structural makeup of natural organic matter plays a major role in regulating its capacity to retain nonionic hydrophobic organic compounds (HOCs). We used a model HOC--phenanthrene--to investigate the correlations between sorption capacity, specifically the modified Freundlich coefficient (K'f), and compositional data of humic acids, humins, and a peat obtained from quantitative 13C solid-state NMR spectroscopy. A positive correlation between K'f and the weight fraction of amorphous poly(methylene) in the sorbents was observed. In contrast, the correlation between phenanthrene sorption capacity and aromaticity or polarity indices of the sorbents was insignificant. The nonpolar aliphatic carbon fraction, excluding poly(methylene), was only partially correlated with K'f. Detailed NMR analyses of the sorbents using 1H inversion-recovery experiments showed that 10-nm diameter domains of branched nonpolar aliphatic groups, which account for 20-50% of all nonpolar aliphatic segments and may be associated with the poly(methylene), were responsible for the partial correlation. The correlation between K'f and the amorphous nonpolar aliphatic domains including amorphous poly(methylene) was strong. The rubbery, relatively low-density, and amorphous nonpolar aliphatic domains can be expected to offer an excellent environment for the sorption of phenanthrene by partitioning. These observations suggest that the domains of amorphous poly(methylene) and branched nonpolar aliphatics, which make up 2-9 wt % of the organic fraction in our samples, may serve as good descriptors for the potential of natural organic matter to retain HOCs in the natural environments.

Sorption of phenanthrene by reference smectites.

Fate and behavior of nonionic hydrophobic organic compounds (HOCs) in the environment is mainly controlled by their interactions with various components of soils and sediments. Due to their large surface area and abundance in many soils, smectites may greatly influence the fate and transport of HOCs in the environment. We used phenanthrene as a probe to explore the potential of reference smectites to sorb HOCs from aqueous solution. Batch experiments were used to construct phenanthrene sorption isotherms, and possible sorption mechanisms were inferred from the shape of the isotherms. Our results demonstrate that smectites can retain large amounts of phenanthrene from water. Phenanthrene sorption capacities of the reference smectites investigated in this study were comparable to those of soil clays containing a considerable amount of organic matter. Hectorite exhibited the highest sorption affinity and capacity followed by Panther Creek montmorillonite. The lack of correlation between Freundlich sorption constants (K'f) and indices of charge or hydrophobicity suggests that sorption of phenanthrene by smectites is primarily a physical phenomenon. Capillary condensation into a network of nanoor micropores created by quasicrystals is likely to be a dominant mechanism of phenanthrene retention by smectites.

Removal of TNT and RDX from water and soil using iron metal.

Contaminated water and soil at active or abandoned munitions plants is a serious problem since these compounds pose risks to human health and can be toxic to aquatic and terrestrial life. Our objective was to determine if zero-valent iron (Fe(0)) could be used to promote remediation of water and soil contaminated with 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). As little as 1% Fe(0) (w/v) removed 70 mg TNT litre(-1) from aqueous solution within 8 h and removed 32 mg RDX litre(-1) within 96 h. Treating slurries (1:5 soil:water) of highly contaminated soil (5200 mg TNT and 6400 mg RDX kg(-1) soil) from the former Nebraska Ordnance Plant (NOP) with 10% Fe(0) (w/w soil) reduced CH(3)CN-extractable TNT and RDX concentrations below USEPA remediation goals (17.2 mg TNT and 5.8 mg RDX kg(-1)). Sequential treatment of a TNT-contaminated solution (70 mg TNT litre(-1) spiked with (14)C-TNT) with Fe(0) (5% w/v) followed by H(2)O(2) (1% v/v) completely destroyed TNT and removed about 94% of the (14)C from solution, 48% of which was mineralized to (14)CO(2) within 8 h. Fe(0)-treated TNT also was more susceptible to biological mineralization. Our observations indicate that Fe(0) alone, Fe(0) followed by H(2)O(2), or Fe(0) in combination with biotic treatment can be used for effective remediation of munitions-contaminated water and soil.