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Benefits associated with the use of municipal biosolids in place of synthetic fertilizers have been repeatedly demonstrated for agronomic crops such as dryland wheat (Triticum). These include increased soil carbon and nitrogen storage, improved yields, and improved soil physical properties including reduced bulk density and increased soil water holding capacity. Use of biosolids has been recognized as a component of a circular economy. Increasingly biosolids-based products are being used in urban areas. Soils in urban areas show similar improvements to soils in agricultural areas after biosolids applications. Research has shown their value for key components of urban greening including tree, turf, ornamental and vegetable growing, green stormwater infrastructure, and reduction in contaminant availability. As the importance of green space in urban areas is increasingly recognized, it is likely that the use of biosolids in these environments will become more common.

The nitrogen (N) release from composted and un-composted biosolids and plant available N (PAN) of the biosolids were quantified to evaluate if composting can contribute to stabilize biosolids N and reduce the nitrate ( NO 3 - ) leaching potential in biosolids-amended soil. Biosolids were composted at >55°C for 21 days after mixing the biosolids with yard waste at 1:1 (w/w) ratio. In the N release study, we installed field lysimeters filled with soil (sand and clay) amended with composted and un-composted biosolids at two rates (30 and 150 dry Mg/ha) and measured the inorganic N in leachate after each rainfall and soil inorganic N monthly. The N released from composted biosolids during the two-year study period were lower (6% of organic N added for clay and 11% for sandy loam soil) as compared to un-composted biosolids (14% of organic N added for clay and 21% for sandy soils). Composted biosolids showed a lower N release rate constant k value of 0.0014 and 0.0027 month-1 for clay and sandy soil, respectively, compared to corresponding values of 0.0035 and 0.0068 month-1 for un-composted biosolids. We used greenhouse bioassay with corn (Zea mays), ryegrass (Lolium perenne), and Miscanthus (Miscanthus giganteus) as test plants grown for six months with reference to N chemical fertilizer ranging from 0, 75, 150 to 300 kg N/ha to evaluate the PAN of the biosolids. Based on our study, plant growth was not affected by using either composted or un-composted biosolids but the PAN was lower in composted biosolids (4.0%-5.9%) than un-composted biosolids (11.4%-13.6%). Composting results in higher N-retention efficiency in biosolids and composted biosolids are a valuable source of N to support the plant growth with lower N released to the environment. Thus, the potential of N leaching would still be low in the situations where a high rate of biosolids needs to be applied for land reclamation or landscaping soil reconstruction. PRACTITIONER POINTS: Composting enhances N-retention efficiency in biosolids and composted biosolids are a valuable source of N to support the plant growth with lower N released to the environment. Potential of N leaching would still be low in the situations where a high rate of biosolids needs to be applied for land reclamation or landscaping soil reconstruction. N released from composted and un-composted biosolids can be adequately described by first-order kinetic model.

The former US Steel Corporation's South Works site in Chicago, IL, is a 230-ha bare brownfield consisting of steel mill slag fill materials that will need to be reclaimed to support and sustain vegetation. We conducted a case study to evaluate the suitability of biosolids and dredged sediments for capping the steel mill slag to establish good quality turfgrass vegetation. Eight study plots were established on a 0.4-ha parcel that received biosolids and dredged sediment blends of 0, 25, 50, or 100% biosolids (v/v). Turfgrass was successfully established and was thicker and greener in biosolids-amended sediments than in unamended sediments. Concentrations of N, P, K, and micronutrients in turfgrass tissues increased with increasing biosolids. Soil organic carbon, N, P, and micronutrients increased with increasing biosolids. Cadmium, Cu, Ni, and Zn concentrations in biosolids-amended sediments also increased with increasing biosolids but were far below phytotoxicity limits for turfgrass. Lead and Cr concentrations in biosolids-amended plots were comparable to concentrations in unamended sediments. Groundwater monitoring lysimeters and wells below the study site and near Lake Michigan were not affected by nutrients leaching from the amendments. Overall, the results from this case study demonstrated that blends of biosolids and dredged sediments could be successfully used for capping steel mill slag brownfield sites to establish good quality turfgrass vegetation.

Large tracts of abandoned urban land, resulting from the deindustrialization of metropolitan areas, are generating a renewed interest among city planners and community organizations envisioning the productive use of this land not only to produce fresh food but to effectively manage stormwater and mitigate the impact of urban heat islands. Healthy and productive soils are paramount to meet these objectives. However, these urban lands are often severely degraded due to anthropogenic activities and are generally contaminated with priority pollutants, especially heavy metals and polycyclic aromatic hydrocarbons. Characterizing these degraded and contaminated soils and making them productive again to restore the required ecosystem services was the theme of the "Soil in the City- 2014" conference organized by W-2170 Committee (USDA's Sponsored Multi-State Research Project: Soil-Based Use of Residuals, Wastewater, & Reclaimed Water). This special section of comprises 12 targeted papers authored by conference participants to make available much needed information about the characteristics of urban soils. Innovative ways to mitigate the risks from pollutants and to improve the soil quality using local resources are discussed. Such practices include the use of composts and biosolids to grow healthy foods, reclaim brownfields, manage stormwater, and improve the overall ecosystem functioning of urban soils. These papers provide a needed resource for educating policymakers, practitioners, and the general public about using locally available resources to restore fertility, productivity, and ecosystem functioning of degraded urban land to revitalize metropolitan areas for improving the overall quality of life for a large segment of a rapidly growing urban population.

Pharmaceutical and personal care product compounds (PPCPs) comprise a large and diverse group of chemical compounds, including prescription and over-the-counter drugs and cleaning agents. Although PPCPs in the effluent and biosolids of water resource recovery facilities (WRRFs) are currently not regulated, public interest has led the Metropolitan Water Reclamation District of Greater Chicago to monitor for 11 PPCPs in the influent, effluent, and biosolids at its seven WRRFs. In 2016, the U.S. Food and Drug Administration (FDA) issued a final rule establishing that 19 specific ingredients, including triclosan and triclocarban, were no longer generally recognized as safe and effective, which prohibits companies from marketing soaps as antibacterial if they contain one or more of these ingredients. It was presumed that since the proposed rulemaking in 2013, manufacturers began to remove these active ingredients from their products. Annual monitoring of 11 PPCPs from 2012 to 2017 demonstrated a 71% decrease in triclosan and 72% decrease in triclocarban in per capita influent loading into seven WRRFs. There was a 70% decrease in triclosan and 80% decrease in triclocarban concentrations in biosolids. These declines suggest the FDA rule for the reduction in use of these compounds was effective and resulted in manufacturers removing these ingredients from their products. PRACTITIONER POINTS: Reduction in triclosan and triclocarban per capita influent loading observed from 2012 to 2017. Reduction in triclosan and triclocarban biosolids loading observed from 2012 to 2017. 2016 FDA rulemaking on antimicrobial soaps was effective in removing triclosan and triclocarban from these products. Positive impact on quality of biosolids land applied to farmland.

The presence of perfluoroalkyl acids (PFAAs) in biosolids-amended and aqueous film-forming foam (AFFF)-impacted soils results in two potential pathways for movement of these environmental contaminants into terrestrial foodwebs. Uptake of PFAAs by earthworms (Eisenia fetida) exposed to unspiked soils with varying levels of PFAAs (a control soil, an industrially impacted biosolids-amended soil, a municipal biosolids-amended soil, and two AFFF-impacted soils) was measured. Standard 28 day exposure experiments were conducted in each soil, and measurements taken at additional time points in the municipal soil were used to model the kinetics of uptake. Uptake and elimination rates and modeling suggested that steady state bioaccumulation was reached within 28 days of exposure for all PFAAs. The highest concentrations in the earthworms were for perfluorooctane sulfonate (PFOS) in the AFFF-impacted Soil A (2160 ng/g) and perfluorododecanoate (PFDoA) in the industrially impacted soil (737 ng/g). Wet-weight (ww) and organic carbon (OC)-based biota soil accumulation factors (BSAFs) for the earthworms were calculated after 28 days of exposure for all five soils. The highest BSAF in the industrially impacted soil was for PFDoA (0.42 goc/gww,worm). Bioaccumulation factors (BAFs, dry-weight-basis, dw) were also calculated at 28 days for each of the soils. With the exception of the control soil and perfluorodecanoate (PFDA) in the industrially impacted soil, all BAF values were above unity, with the highest being for perfluorohexanesulfonate (PFHxS) in the AFFF-impacted Soil A (139 gdw,soil/gdw,worm). BSAFs and BAFs increased with increasing chain length for the perfluorocarboxylates (PFCAs) and decreased with increasing chain length for the perfluoroalkyl sulfonates (PFSAs). The results indicate that PFAA bioaccumulation into earthworms depends on soil concentrations, soil characteristics, analyte, and duration of exposure, and that accumulation into earthworms may be a potential route of entry of PFAAs into terrestrial foodwebs.

Crop uptake of perfluoroalkyl acids (PFAAs) from biosolids-amended soil has been identified as a potential pathway for PFAA entry into the terrestrial food chain. This study compared the uptake of PFAAs in greenhouse-grown radish (Raphanus sativus), celery (Apium graveolens var. dulce), tomato (Lycopersicon lycopersicum), and sugar snap pea (Pisum sativum var. macrocarpon) from an industrially impacted biosolids-amended soil, a municipal biosolids-amended soil, and a control soil. Individual concentrations of PFAAs, on a dry weight basis, in mature, edible portions of crops grown in soil amended with PFAA industrially impacted biosolids were highest for perfluorooctanoate (PFOA; 67 ng/g) in radish root, perfluorobutanoate (PFBA; 232 ng/g) in celery shoot, and PFBA (150 ng/g) in pea fruit. Comparatively, PFAA concentrations in edible compartments of crops grown in the municipal biosolids-amended soil and in the control soil were less than 25 ng/g. Bioaccumulation factors (BAFs) were calculated for the root, shoot, and fruit compartments (as applicable) of all crops grown in the industrially impacted soil. BAFs were highest for PFBA in the shoots of all crops, as well as in the fruit compartment of pea. Root-soil concentration factors (RCFs) for tomato and pea were independent of PFAA chain length, while radish and celery RCFs showed a slight decrease with increasing chain length. Shoot-soil concentration factors (SCFs) for all crops showed a decrease with increasing chain length (0.11 to 0.36 log decrease per CF2 group). The biggest decrease (0.54-0.58 log decrease per CF2 group) was seen in fruit-soil concentration factors (FCFs). Crop anatomy and PFAA properties were utilized to explain data trends. In general, fruit crops were found to accumulate fewer long-chain PFAAs than shoot or root crops presumably due to an increasing number of biological barriers as the contaminant is transported throughout the plant (roots to shoots to fruits). These data were incorporated into a preliminary conceptual framework for PFAA accumulation in edible crops. In addition, these data suggest that edible crops grown in soils conventionally amended for nutrients with biosolids (that are not impacted by PFAA industries) are unlikely a significant source of long-chain PFAA exposure to humans.

Promulgation of the Clean Water Act (CWA) authorized the United States Environmental Protection Agency (U.S. EPA) to regulate quality standards for surface waters and establish regulations limiting the amounts and types of pollutants entering the nation's waters. U.S. EPA imposed national pretreatment standards on industrial wastes discharged to the collection systems of publicly owned treatment works (POTWs) and promulgated General Pretreatment Regulations in 1978. This study analyzed trace metals data from the National Sewage Sludge Surveys conducted by U.S. EPA and the American Metropolitan Sewage Agencies (AMSA) to evaluate the effect of implementation of the national industrial pretreatment standards on concentrations of trace metals in sludges generated by POTWs in the United States. The data showed that implementation of pretreatment programs has been highly effective in reducing the amount of pollutants that enter POTWs and has resulted in a substantial reduction in the levels of trace metals in the municipal sludges. Concentrations of chromium, lead, and nickel in sludge declined by 78, 73, and 63%, respectively, within a year after promulgation of General Pretreatment Regulations. Resulting from these measures, metal concentrations in the sludges generated by a majority of POTWs in the United States are sufficiently low that the sludges can be classified as biosolids and also meet the U.S. EPA's exceptional quality criteria for trace metals in biosolids. This improvement gives POTWs the option to use their biosolids beneficially through land application.

The presence of perfluoroalkyl acids (PFAAs) in biosolids destined for use in agriculture has raised concerns about their potential to enter the terrestrial food chain via bioaccumulation in edible plants. Uptake of PFAAs by greenhouse lettuce ( Lactuca sativa ) and tomato ( Lycopersicon lycopersicum ) grown in an industrially impacted biosolids-amended soil, a municipal biosolids-amended soil, and a control soil was measured. Bioaccumulation factors (BAFs) were calculated for the edible portions of both lettuce and tomato. Dry weight concentrations observed in lettuce grown in a soil amended (biosolids:soil dry weight ratio of 1:10) with PFAA industrially contaminated biosolids were up to 266 and 236 ng/g for perfluorobutanoic acid (PFBA) and perfluoropentanoic acid (PFPeA), respectively, and reached 56 and 211 ng/g for PFBA and PFPeA in tomato, respectively. BAFs for many PFAAs were well above unity, with PFBA having the highest BAF in lettuce (56.8) and PFPeA the highest in tomato (17.1). In addition, the BAFs for PFAAs in greenhouse lettuce decreased approximately 0.3 log units per CF2 group. A limited-scale field study was conducted to verify greenhouse findings. The greatest accumulation was seen for PFBA and PFPeA in both field-grown lettuce and tomato; BAFs for PFBA were highest in both crops. PFAA levels measured in lettuce and tomato grown in field soil amended with only a single application of biosolids (at an agronomic rate for nitrogen) were predominantly below the limit of quantitation (LOQ). In addition, corn ( Zea mays ) stover, corn grains, and soil were collected from several full-scale biosolids-amended farm fields. At these fields, all PFAAs were below the LOQ in the corn grains and only trace amounts of PFBA and PFPeA were detected in the corn stover. This study confirms that the bioaccumulation of PFAAs from biosolids-amended soils depends strongly on PFAA concentrations, soil properties, the type of crop, and analyte.

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.

Desorption and dissolution often control the mobility and availability of phosphorus (P) in the natural environment. In this study, P desorption was compared from a soil receiving either long-term inorganic or biosolid fertilization as a part of a long-term field scale research project. A co

Polybrominated diphenyl ethers (PBDEs) have been used extensively to flame-retard polymers and textiles. These persistent chemicals enter wastewater streams following manufacture, use, and disposal, concentrating in the settled solids during treatment. Land application of stabilized sewage sludge (known as biosolids) can contribute PBDEs to terrestrial systems. Monitoring sludge/biosolids contaminant burdens may be valuable in revealing trends in societal chemical usage and environmental release. In archived Chicago area sludges/biosolids from 1975 to 2008, penta-BDE concentrations increased and then plateaued after about 2000. Penta-BDE manufacture in the United States ended in December 2004. Deca-BDE concentrations in biosolids rose from 1995 to 2008, doubling on a 5-year interval. Evaluation of U.S. Environmental Protection Agency Targeted National Sewage Sludge Survey data from 2006 to 2007 revealed highest penta-BDE biosolids levels from western and lowest from northeastern wastewater treatment plants (2120 and 1530 μg/kg, respectively), consistent with patterns reported in some recent indoor dust and human blood studies. No significant regional trends were observed for deca-BDE concentrations. Congener patterns in contemporary Chicago biosolids support the contention that BDE-209 can be dehalogenated to less brominated congeners. Biosolids application on agricultural fields increased PBDE soil concentrations. However, corn grown thereon did not exhibit measurable PBDE uptake; perhaps due to low bioavailability of the biosolids-associated flame retardants.

Sequential chemical extraction is a common analytical approach used to separate soil P into operationally defined fractions based on solubility in increasingly strong extractants. However, there are some concerns that the relationship between these operationally defined pools and the true ch

The recently discovered ammonia-oxidizing archaea (AOA) have been suggested as contributors to the first step of nitrification in terrestrial ecosystems, a role that was previously assigned exclusively to ammonia-oxidizing bacteria (AOB). The current study assessed the effects of agricultural management, specifically amendment of soil with biosolids or synthetic fertilizer, on nitrification rates and copy numbers of archaeal and bacterial ammonia monooxygenase ( amoA ) genes. Anaerobically digested biosolids or synthetic fertilizer was applied annually for three consecutive years to field plots used for corn production. Biosolids were applied at two loading rates, a typical agronomic rate (27 Mg hectare −1 year −1 ) and double the agronomic rate (54 Mg hectare −1 year −1 ), while synthetic fertilizer was applied at an agronomic rate typical for the region (291 kg N hectare −1 year −1 ). Both biosolids amendments and synthetic fertilizer increased soil N and corn yield, but only the biosolids amendments resulted in significant increases in nitrification rates and increases in the copy numbers of archaeal and bacterial amoA genes. In addition, only archaeal amoA gene copy numbers increased in response to biosolids applied at the typical agronomic rate and showed a significant correlation with nitrification rates. Finally, copy numbers of archaeal amoA genes were significantly higher than copy numbers of bacterial amoA genes for all treatments. These results implicate AOA as being primarily responsible for the increased nitrification observed in an agricultural soil amended with biosolids. These results also support the hypothesis that physiological differences between AOA and AOB may enable them to occupy distinct ecological niches.

Detectable levels of dioxins have been reported in biosolids, but very little information is available on the effect of long-term application of biosolids on dioxins accumulation in soil and uptake by plants. We analyzed dioxins in soil and corn tissue samples from field plots after 30 continuous applications of biosolids at 0 (Control), 16.8, and 67.2 Mg biosolids ha(-1) yr(-1) resulting in 0, 504, and 2016 Mg ha(-1) cumulative loadings of biosolids, respectively. The levels of dioxins in soil were only 79.9, 115.5, and 247.5 ng toxic equivalents (TEQs) kg(-1) in the 0, 504, and 2016 Mg biosolids ha(-1) plots, respectively. Dioxins were not detected in the corn grain, and only trace levels (6.8-7.5 ng TEQs kg(-1)) were found in the corn stover; however, these values were not statistically different between control and biosolids-amended soils. These observations suggest that although long-term application of biosolids may increase the levels of dioxins in soil, it does not affect dioxins uptake by corn.

Restoration of the Illinois River and its backwater lakes involves the dredging of millions of cubic meters of sediment, and the relocation of this dredged sediment is a significant challenge. Beneficial use of sediment as landscaping soil on brownfields, strip mines, highway borders and other areas is a potential use for large quantities of this material, as sediments have desirable soil characteristics, including a favorable texture for plant growth and good water holding capacity. The addition of biosolids to Illinois River sediments has the potential to increase the organic and nutrient content of the sediments and thus to make these sediments more useful for the reclamation of damaged soils. The goal of the current study was to assess the impacts of biosolids additions on the physical/chemical characteristics and microbial communities of surface applied river sediments. Field plots containing various sediment/biosolids mixture were established and examined 1 year after application. Results indicated that biosolids addition had significant positive effects on soil organic carbon, total Kjeldahl nitrogen, total phosphorous, and microbial biomass and activity. In addition, the sediment/biosolids mixtures showed lower salinity and lower concentrations of copper, lead and zinc than the pure biosolids. PLFA analysis revealed that biosolids addition resulted in shifts in microbial community composition, with relative increases in Gram negative bacteria and relative decreases in Gram positive bacteria, fungi, and actinomycetes. These data suggest that a mixture of sediment and biosolids is preferable to either sediment or biosolids alone.

To explore the hypothesis that enrichment of decomposition-resistant compounds might vary in humic acid (HA) that is associated with silt and clay-size microaggregates, we used infrared spectroscopy, thermal analyses, nuclear magnetic resonance spectroscopy, and pyrolysis techniques to characterize the functional groups and structures of HA isolated from coarse silt and clay fractions of two Iowa Mollisols. Samples from the A horizons of Sparta (a sandy, mixed, mesic Entic Hapludoll) and Zook (a fine, smectitic, mesic Cumulic Vertic Endoaquoll) soils were gently dispersed and divided into silt and clay fractions before HA was extracted by standardized techniques. The FTIR, thermal, and NMR analyses revealed that HA in the sandy, well-drained Sparta soil and size fractions was enriched in aliphatic compounds, readily oxidizable carbohydrates, and lignin compared with HA in the poorly drained, clayey Zook soil. Moreover, pyrolysis spectra demonstrated that fatty acids in the Sparta HAs had longer chain lengths than those of the Zook HAs. Clay-fraction HA contained more readily oxidizable components and aliphatic moieties than did silt-fraction HA. The NMR-derived observation that Zook soil HA contained more charcoal-like moieties than Sparta HA was also consistent with the greater amounts of combustion-resistant material observed in the thermal analyses of Zook HA. Others have shown that “whole” soil organic matter characteristics differ with the size of the aggregates and particles that the organic matter is associated with. For these prairie-derived soils, our study confirms and deepens this observation specifically for HA associated with particle-size fractions.

Permeable pavements are being adopted as a green solution in many parts of the world to manage urban stormwater quantity and quality. This paper reports on the measured in-situ infiltration performance over a four-year period since construction and use of three permeable parking sections (permeable pavers, permeable concrete and permeable asphalt) of an employee car parking lot. There was only a marginal decline in infiltration rates of all three pavements after one year of use. However, between years two to four, the infiltration rates declined significantly due to clogging of pores either by dry deposition of particles and/or shear stress of vehicles driving and degrading the permeable surfaces; during the last two years, a greater decline was also observed in driving areas of the parking lots compared to parking slots, where minimal wear and tear are expected. Maintenance strategies were employed to reclaim some of the lost infiltration rate of the permeable pavements to limited success. Despite this decline, the infiltration rates were still four to five times higher than average rainstorm intensity in the region. Thus, these permeable pavement parking lots may have significant ecological importance due to their ability to infiltrate rainwater quickly, reduce the runoff in the catchment area, and also dampen runoff peak flows that could otherwise enter the collection system for treatment in a combined sewer area.

Significant concentrations of chlorinated pesticides such as 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) and its two main transformation products, 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE) are still present in soil and sediment systems more than 30 years after DDT use was banned in the United States. DDT enters waterways via the runoff from industrial point sources, agricultural lands and atmospheric deposition. We evaluated zero-valent iron (Fe 0 ), ferrous sulfide (FeS), as well as combining them with hydrogen peroxide (H 2 O 2 ) as viable treatment technologies for degrading DDT in an aqueous solution. Treatment of DDT with Fe 0 and FeS resulted in approximately 88% and 56% transformation of DDT within 150 h, respectively. DDE production was insignificant in all systems. The DDT removal was slower with FeS than with Fe 0 , but the amounts of DDD and DDE produced did not exceed baseline. Treatment with a 1:1 mixture of Fe 0 –FeS removed about 95% of the added mass of DDT within 4 days and generated significant amounts of DDD and minor amounts of DDMU. When small amounts of H 2 O 2 were introduced halfway through the Fe 0 and FeS treatment times, the mass of DDT decreased by 87% and 96%, respectively, within 2 days. Our results demonstrate that mixtures of Fe 0 –FeS in combination with H 2 O 2 can be used for rapid and efficient removal of DDT from aqueous solutions.

This work looks at several new abiotic treatment methods for transformation of DDT in an aqueous solution. Various combinations of calcium peroxide (Ca O2 ) , zero-valent iron ( Fe0 ) , iron sulfide (FeS), and hydrogen peroxide ( H2 O2 ) were utilized to promote the abiotic transformation of 1,1,1-trichloro-2,2-bis( p -chlorophenyl)ethane (DDT) in electrolyte, hydroquinone, and nonionic surfactant (Triton X-114) systems. Treatment with Ca O2 resulted in 86% DDT mass reduction within 10 days of treatment with only traces of 1,1-dichloro-2,2-bis( p -chlorophenyl)ethane (DDD) , 1,1-dichloro-2,2-bis( p -chlorophenyl)ethylene (DDE), and 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDMU) being generated. Treatments with 1:1 mixtures of Fe0 :Ca O2 and FeS:Ca O2 resulted in 86 and 85% DDT mass transformation, respectively, within 8 days . A mixture of 0.75 g Fe0 :0.1 g Ca O2 showed similar results with 79% DDT mass transformed within 8 days . A mixture of 0.75–0.1 g of Fe0 :FeS resulted in 85 and 97% transformat...

This study was conducted to estimate nitrogen (N) mineralization of anaerobically digested centrifuge cake from the Stickney Water Reclamation Plant (SWRP) and Calumet Water Reclamation Plant (CWRP), lagoon-aged air-dried biosolids from the CWRP, and Milorganite at three rates of application (0, 12.5 and 25 Mg ha(-1)). The N mineralized varied among biosolids as follows: Milorganite (44%) > SWRP centrifuge cake (35%) > CWRP centrifuge cake (31%) > aged air-dried (13%). The N mineralized in the SWRP cake (32%) and CWRP aged air-dried biosolids (12%) determined from the 15N study were in agreement with the first study. The N mineralization value for centrifuge cake biosolids observed in our study is higher than the value given in the Part 503 rule and Illinois Part 391 guidelines. These results will be used to fine-tune biosolids application rate to match crop N demand without compromising yield while minimizing any adverse effect on the environment.

Topsoil removal, compaction, and other practices in urban and industrial landscapes can degrade soil and soil ecosystem services. There is growing interest to remediate these for recreational and residential purposes, and urban waste materials offers potential to improve degraded soils. Therefore, the objective of this study was to compare the effects of urban waste products on microbial properties of a degraded industrial soil. The soil amendments were vegetative yard waste compost (VC), biosolids (BioS), and a designer mix (DM) containing BioS, biochar (BC), and drinking water treatment residual (WTR). The experiment had a completely randomized design with following treatments initiated in 2009: control soil, VC, BioS-1 (202 Mg ha(-1)), BioS-2 (403 Mg ha(-1)), and DM (202 Mg BioS ha(-1) plus BC and WTR). Soils (0-15-cm depth) were sampled in 2009, 2010, and 2011 and analyzed for enzyme activities (arylsulfatase, β-glucosaminidase, β-glucosidase, acid phosphatase, fluorescein diacetate, and urease) and soil microbial community structure using phospholipid fatty acid analysis (PLFA). In general, all organic amendments increased enzyme activities in 2009 with BioS treatments having the highest activity. However, this was followed by a decline in enzyme activities by 2011 that were still significantly higher than control. The fungal PLFA biomarkers were highest in the BioS treatments, whereas the control soil had the highest levels of the PLFA stress markers (P 0.10). In conclusion, one-time addition of VC or BioS was most effective on enzyme activities; the BioS treatment significantly increased fungal biomass over the other treatments; addition of BioS to soils decreased microbial stress levels; and microbial measures showed no statistical differences between BioS and VC treatments after 3 years of treatment.

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.

To better understand the chemistry of S-containing ligands in biosolids-derived fulvic acid (BFA), we used selective dissolution analysis and X-ray absorption near-edge structure (XANES) spectroscopy to estimate major classes of S (oxidized and reduced S) and oxidation states of S in BFA, respectively. The BFA was fractionated into two classestotal hydrophilic and hydrophobic acid fractionsusing XAD-8 resin and into molecular-weight classes by dialysis. The selective dissolution analyses show that oxidized S was the dominant class of S in the total hydrophilic fraction, whereas reduced S was dominant in the hydrophobic acid fraction. The XANES analyses also indicated that oxidized forms of S were dominant in the total hydrophilic fraction, whereas reduced forms of S were dominant in the hydrophobic acid fraction. BFA fractions separated by XAD-8 resin and dialysis contained distinct classes and oxidation states of S. The XANES analyses not only corroborated the traditional selective dissolution approaches...

Prediction of the fate of hydrophobic organic compounds (HOCs) in the soil environment is difficult due to the highly complex interaction between the organic molecules and the soil components. The Freundlich isotherm is the most commonly used model to describe retention of HOCs by heterogeneous sorbents. Because of inconsistent units of constants calculated from the Freundlich model, it is difficult to strictly compare the sorption of organic molecules by different sorbents. In this study, we modified the Freundlich equation to better assess the effects of organic carbon content and physical heterogeneity on the sorption of HOCs by soils and microaggregate fractions, using naphthalene and phenanthrene as probes. Isotherms for naphthalene and phenanthrene sorption were nonlinear and well described by the Freundlich equation. Unit-equivalent Freundlich coefficients (K‘f) were calculated by normalizing the liquid-phase equilibrium concentrations (Ce) to the supercooled liquid-state solubility (Sscl) of napht...

Atrazine is the most widely used herbicide in the U.S. and has been detected in surface water and groundwater. Technologies are needed for onsite and in situ remediation of water and soil containing atrazine. We investigated the potential of using fine-grained, zero-valent iron (Fe0) to remove atrazine and promote its degradation in contaminated water and soil. Atrazine loss from aqueous solution increased with increasing Fe0concentration (w/v). Agitating 20 μg14C-ring-labeled atrazine L−1with 10% Fe0(w/v) removed 92% of the14C from solution within 48 h. Only about 4% of the14C lost from solution was extractable from the iron with 3 mM CaCl2(readily available pool), 81% was extractable with CH3CN (potentially available pool), and 11% was unextractable residues. A companion experiment indicated that most of the14C extracted from the iron with 3 mM CaCl2after the 48-h Fe0treatment was unaltered atrazine, while the CH3CN extract contained approximately 33% atrazine and 48% was unidentified atrazine transformation products. Treating a highly contaminated solution (20 mg atrazine L−1) with 20% Fe0(w/v) removed 88% of the14C (added as14C-ring-labeled atrazine) from solution within 48 h. Deethylatrazine was the main atrazine transformation product detected in solution after treatment, but small amounts of deisopropylatrazine, didealkylatrazine, and hydroxyatrazine were also found. Treating Sharpsburg surface soil containing 1 mg atrazine kg−1with Fe0(2%, w/w) increased atrazine mineralization from 4.1 to 11.2% after 120 d. Pyrite (4% FeS2, w/w) also increased atrazine mineralization in surface soil, but was less effective in the presence of NO3−or SO42−(100 mg kg−1soil). Adding 2% Fe0(w/w) and 100 mg NO3−kg−1to contaminated subsurface soil increased atrazine mineralization from 0.4 to 8.2% within 120 d, and unextractable residues increased from 4.6 to 9.8%. These results indicate iron can sorb atrazine and promote its transformation in water and soil.

Soils surrounding former munitions production facilities are highly contaminated with 2,4,6-trinitrotoluene (TNT). Long-term availability and fate of TNT and its transformation products must be understood to predict environmental impact and develop appropriate remediation strategies. Sorption and transport in surface soil containing solidphase TNT are particularly critical, since nonlinear sorption isotherms indicate greater TNT availability for transport at high concentrations. Our objectives were to determine long-term sorption and bound residue formation in surface and subsurface Sharpsburg soil (Typic Argiudoll). Prolonged equilibration of ¹⁴C-TNT with the soil revealed a gradual increase in amount sorbed and formation of unextractable (bound) ¹⁴C residues. The presence of solid-phase TNT did not initially affect the amount of ¹⁴C sorbed during a 168-d equilibration. After 168 d, 93% of the added ¹⁴C was sorbed by uncontaminated soil, while 79% was sorbed by soil containing solid-phase TNT. In the absence of solid phase, pools of readily available (extractable with 3 mM CaCl₂) and potentially available (CH₃CN-extractable) sorbed TNT decreased rapidly with time and coincided with increased ¹⁴C in soil organic matter. More ¹⁴C was found in fulvic acid than in the humic acid fraction when no solid-phase TNT was present. After sequential extractions, including strong alkali and acid, 32 to 40% of the sorbed ¹⁴C was irreversibly bound (unextractable) in Sharpsburg surface and subsurface soil. Results provide strong evidence for humification of TNT in soil. This process may represent a significant route for detoxification in the soil-water environment. Publication no. 11551, Agric. Res. Div., Univ. of Nebraska — Lincoln, Lincoln, NE 68583-0915.

Past disposal practices at munitions production plants have contaminated terrestrial and aquatk ecosystems with 2,4,6-trinitrotoluene (TNT). We determined TNT transport, degradation, and long-term sorption characteristics in soil. Transport experiments were conducted with repacked, unsaturated soil columns containing uncontaminated soil or layers of contaminated and uncontaminated soil. Uncontaminated soil columns received multiple pore volumes (22-50) of a TNT-{sup 3}H{sub 2}O pulse, containing 70 or 6.3 mg TNT L{sup -1} at a constant pore water velocity. TNT breakthrough curves (BTCs) never reached initial solute pulse concentrations. Apex concentrations (C/C{sub o}) were between 0.6 and 0.8 for an initial pulse of 70 mg TNT L{sup -1} and 0.2 to 0.3 for the 6.3 mg TNT L{sup -1} pulse. Earlier TNT breakthrough was observed at the higher pulse concentration. This mobility difference was predicted from the nonlinear adsorption isotherm determined for TNT sorption. In all experiments, a significant fraction of added TNT was recovered as amino degradates of TNT. Mass balance estimates indicated 81% of the added TNT was recovered (as TNT and amino degradates) from columns receiving the 70 mg TNT L{sup -1} pulse compared to 35% from columns receiving the 6.3 mg TNT L{sup -1} pulse. Most of the unaccountable TNT wasmore » hypothesized to be unextractable. This was supported by a 168-d sorption experiment, which found that within 14d, 80% of {sup 14}C activity (added as {sup 14}C-TNT) was adsorbed and roughly 40% unextractable. Our observations illustrate that TNT sorption and degradation are concentration-dependent and the assumptions of linear adsorption and adsorption-desorption singularity commonly used in transport modeling, may not be valid for predicting TNT transport in munitions-contaminated soils. 29 refs., 6 figs., 7 tabs.« less

The presence of the antimicrobial chemicals triclocarban (TCC) and triclosan (TCS) in municipal biosolids has raised concerns about the potential impacts of these chemicals on soil ecosystems following land application of municipal biosolids. The relative persistence of TCC and TCS in agricultural fields receiving yearly applications of biosolids at six different loading rates over a three-year period was investigated. Soil and biosolids samples were collected, extracted, and analyzed for TCC and TCS using liquid chromatography–tandem mass spectrometry. In addition, the potential for bioaccumulation of TCC and TCS from the biosolids-amended soils was assessed over 28 d in the earthworm Eisenia foetida. Standard 28-d bioaccumulation tests were conducted for three biosolids loading rates from two sites, representing agronomic and twice the agronomic rates of biosolids application plots as well as control plots receiving no applications of biosolids. Additional bioaccumulation kinetic data were collected for the soils receiving the high biosolids loadings to ensure attainment of quasi steady-state conditions. The results indicate that TCC is relatively more persistent in biosolids-amended soil than TCS. In addition, TCC bioaccumulated in E. foetida, reaching body burdens of 25 ± 4 and 133 ± 17 ng/gww in worms exposed for 28 d to the two soils amended with biosolids at agronomic rates. The 28-d organic carbon and lipid-normalized biota soil accumulation factors (BSAFs) were calculated for TCC and ranged from 0.22 ± 0.12 to 0.71 ± 0.13. These findings suggest that TCC bioaccumulation is somewhat consistent with the traditional hydrophobic organic contaminant (HOC) partitioning paradigm. However, these data also suggest substantially reduced bioavailability of TCC in biosolids-amended soils compared with HOC partitioning theory. Environ. Toxicol. Chem. 2011; 30:556–563. © 2011 SETAC

Land application of biosolids is a common practice throughout the world. However, concerns continue to be raised about the safety of this practice, because biosolids may contain trace levels of organic contaminants. The present study evaluated the levels of triclocarban (TCC), triclosan (TCS), 4-nonylphenol (4-NP), and polybrominated diphenyl ethers (PBDEs) in biosolids from 16 wastewater treatment plants and in soils from field plots receiving annual applications of biosolids for 33 years. All of the four contaminants evaluated were detected in most of the biosolids at concentrations ranging from hundreds of µg/kg to over 1,000 mg/kg (dry wt basis). They were detected at µg/kg levels in the biosolids-amended soil, but their concentrations decreased sharply with increasing soil depth for 4-NP, PBDEs, and TCC, indicating limited soil leaching of those compounds. However, potential leaching of TCS in the biosolids-amended soils was observed. The levels of all four compounds in the surface soil increased with increasing biosolids application rate. Compared with the estimated 33-year cumulative input to the soil during the 33-year consecutive biosolids application, most of the PBDEs and a small percentage of 4-NP, TCC, and TCS remained in the top 120-cm soil layer. These observations suggest slow degradation of PBDEs but rapid transformation of 4-NP, TCC, and TCS in the biosolids-amended soils. Environ. Toxicol. Chem. 2010;29:597–605. © 2009 SETAC

Biosolids-borne trace elements may be released to the environment when biosolids are used as fertilizers in farm land. Trace element leachate concentrations from biosolids are known to be limited by both organic and inorganic sorbent surfaces; this experimental evidence has not been previously verified with geochemical modeling of sorption reactions. In this study, pH-dependent leaching experiments and sorption isotherm experiments were coupled with a multisurface geochemical modeling approach. Biosolids samples were obtained from Toledo and Chicago wastewater treatment plants; their sorbent surfaces were defined and modeled as a combination of organic matter (OM) and Fe-, Al-, and Mn-oxides. The multisurface geochemical modeling approach was partially successful in predicting the pH-dependent leachate concentrations of As, Cd, Cr, Cu, Mo, Ni, and Zn. Both modeled and experimental data indicated that As and Mo in biosolids were bound to Fe- oxides; Cd, Cr, and Cu were bound mainly to OM; and as pH increased the fractions of Cd and Cu bound to Fe- oxides in the biosolids matrix increased. Ni and Zn were distributed between OM and Fe- oxides, and the percentage of each fraction depended on the pH. This study showed that the multisurface geochemical model could be used to generate As (and to a lesser extent Cd) Freundlich isotherm parameters for biosolids. However, the composition and reactivity of solid and dissolved OM was identified as a source of uncertainty in the modeling results. Therefore, more detailed studies focusing on the reactivity of isolated biosolids OM fractions with regard to proton and metal binding are needed to improve the capability of geochemical models to predict the fate of biosolids-borne trace metals in the environment. QC 20101129

Soil solution chemistry influences the sorption and transport behavior of hydrophobic organic compounds (HOCs) in soil. We used both batch and column studies to investigate the influence of ionic strengths (0.03 and 1.5 M) and flow velocities (12 and 24 cm h-1) on sorption and transport of naphthalene (NAP) in aggregated soil. Sorption parameters such as the Freundlich coefficient (Kf) and exponent (n) calculated from batch studies and column experiments were also compared. Retardation of NAP transport was greater at higher solution ionic strength, which may be attributed to greater sorption affinity due to enhanced aggregation of the sorbent. The effect of ionic strength on sorption of NAP observed in the batch study was consistent with the results from the column study. The Kf and n values obtained from the batch study for the two ionic strengths ranged from 7.8 to 13.7 and 0.68 to 0.80, respectively, whereas the Kf and n values obtained from the column study ranged from 7.9 to 9.9 and 0.73 to 0.85, respectively. The effluent breakthrough curve (BTC) of NAP at a flow rate of 24 cm h-1 showed significant chemical and physical nonequilibrium behavior, implying that a considerable amount of sorption in aggregated soil was time dependent when flow was relatively fast. The BTCs calculated with the parameters determined from batch studies compared poorly with the measured BTCs. The potential for nonequilibrium transport should be incorporated in models used for predicting the fate and transport of HOCs. Furthermore, caution is required when extrapolating the results from batch studies, especially for aggregated soils.

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.