Quantifying Antibiotic Distribution in Solid and Liquid Fractions of Manure Using a Two-Step, Multi-Residue Antibiotic Extraction.

Antibiotic distribution and analysis within liquid and solid fractions of manure are highly variable due to each compound's respective physiochemical properties. This study developed and evaluated a uniform method extracting 10 antibiotics from 4 antibiotic classes (tetracycline, sulfonamides, macrolides, and ß-lactam) from unprocessed manure, solid−liquid separated manure, and composted solids. Through systematic manipulation of previously published liquid chromatography tandem mass spectrometry methods; this study developed an extraction protocol with optimized recovery efficiencies for varied manure substrates. The method includes a two-step, liquid-solid extraction using 10 mL of 0.1 M EDTA-McIlviane buffer followed by 10 mL of methanol. Antibiotics recoveries from unprocessed manure, separated liquids, separated solids, and heat-treated solids using the two-step extraction method had relative standard deviations < 30% for all but ceftiofur. Total antibiotic recoveries were 67−131% for tetracyclines, 56% for sulfonamide, 49−53% for macrolides, and 1.3−66% for ß-lactams. This is the first study to use one protocol to assess four classes of antibiotics in liquid and solid manure fractions. This study allowed for more precise risk assessment of antibiotic transport in manure waste stream applied to fields as a liquid or solid compost.

Trans enantiomeric separation of MESA and MOXA, two environmentally important metabolites of the herbicide, metolachlor.

Complete separation of the trans-enantiomers of the two most abundant, persistent polar metabolites of metolachlor, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA), was achieved using UPLC equipped with a reverse phase chiral column and trace detection with an electrospray triple quadrupole mass spectrometer. Various conditions that influenced the separation and instrumental signal were investigated to achieve the optimum separation and instrument response within an analysis time of less than 30 minutes. Different eluting solvent compositions for each metabolite were required for optimized separation of of the 4 enantiomers. Standard curves were responsive to less than 13 ng/mL and 8 ng/mL for the least plentiful MOXA and MESA enantiomers, respectively with a linear coefficient of determination greater than 0.998. Suitability of the method for quantification of the 4 mixed enantiomers of each was demonstrated using natural surface water samples collected from the Choptank River watershed in Eastern Maryland.•LC chiral separation parameters were varied to achieve optimal separation of the major enantiomers of the two metolachlor metabolites.•LC/MS-MS parameters were adjusted to maximize response and minimize analysis time.•Finished methods were used to quantitate enantiomers in archived stream water extracts from agricultural watersheds with corn/soybean production.

Toxicological responses to sublethal anticoagulant rodenticide exposure in free-flying hawks.

An important component of assessing the hazards of anticoagulant rodenticides to non-target wildlife is observations in exposed free-ranging individuals. The objective of this study was to determine whether environmentally realistic, sublethal first-generation anticoagulant rodenticide (FGAR) exposures via prey can result in direct or indirect adverse effects to free-flying raptors. We offered black-tailed prairie dogs (Cynomys ludovicianus) that had fed on Rozol® Prairie Dog Bait (Rozol, 0.005% active ingredient chlorophacinone, CPN) to six wild-caught red-tailed hawks (RTHA, Buteo jamaicensis), and also offered black-tailed prairie dogs that were not exposed to Rozol to another two wild-caught RTHAs for 7 days. On day 6, blood was collected to determine CPN's effects on blood clotting time. On day 7, seven of the eight RTHAs were fitted with VHF radio telemetry transmitters and the RTHAs were released the following day and were monitored for 33 days. Prothrombin time (PT) and Russell's viper venom time confirmed that the CPN-exposed RTHAs were exposed to and were adversely affected by CPN. Four of the six CPN-exposed RTHAs exhibited ptiloerection, an indication of thermoregulatory dysfunction due to CPN toxicity, but no signs of intoxication were observed in the reference hawk or the remaining two CPN-exposed RTHAs. Of note is that PT values were associated with ptiloerection duration and frequency; therefore, sublethal CPN exposure can directly or indirectly evoke adverse effects in wild birds. Although our sample sizes were small, this study is a first to relate coagulation times to adverse clinical signs in free-ranging birds.

Electrocardiographic Diagnosis of Acute Coronary Occlusion Myocardial Infarction in Ventricular Paced Rhythm Using the Modified Sgarbossa Criteria.

STUDY OBJECTIVE: Ventricular paced rhythm is thought to obscure the electrocardiographic diagnosis of acute coronary occlusion myocardial infarction. Our primary aim was to compare the sensitivity of the modified Sgarbossa criteria (MSC) to that of the original Sgarbossa criteria for the diagnosis of occlusion myocardial infarction in patients with ventricular paced rhythm. METHODS: In this retrospective case-control investigation, we studied adult patients with ventricular paced rhythm and symptoms of acute coronary syndrome who presented in an emergency manner to 16 international cardiac referral centers between January 2008 and January 2018. The occlusion myocardial infarction group was defined angiographically as thrombolysis in myocardial infarction grade 0 to 1 flow or angiographic evidence of coronary thrombosis and peak cardiac troponin I ≥10.0 ng/mL or troponin T ≥1.0 ng/mL. There were 2 control groups: the "non-occlusion myocardial infarction-angio" group consisted of patients who underwent coronary angiography for presumed type I myocardial infarction but did not meet the definition of occlusion myocardial infarction; the "no occlusion myocardial infarction" control group consisted of randomly selected emergency department patients without occlusion myocardial infarction. RESULTS: There were 59 occlusion myocardial infarction, 90 non-occlusion myocardial infarction-angio, and 102 no occlusion myocardial infarction subjects (mean age, 72.0 years; 168 [66.9%] men). For the diagnosis of occlusion myocardial infarction, the MSC were more sensitive than the original Sgarbossa criteria (sensitivity 81% [95% confidence interval [CI] 69 to 90] versus 56% [95% CI 42 to 69]). Adding concordant ST-depression in V4 to V6 to the MSC yielded 86% (95% CI 75 to 94) sensitivity. For the no occlusion myocardial infarction control group of ED patients, additional test characteristics of MSC and original Sgarbossa criteria, respectively, were as follows: specificity 96% (95% CI 90 to 99) versus 97% (95% CI 92 to 99); negative likelihood ratio (LR) 0.19 (95% CI 0.11 to 0.33) versus 0.45 (95% CI 0.34 to 0.65); and positive LR 21 (95% CI 7.9 to 55) versus 19 (95% CI 6.1 to 59). For the non-occlusion myocardial infarction-angio control group, additional test characteristics of MSC and original Sgarbossa criteria, respectively, were as follows: specificity 84% (95% CI 76 to 91) versus 90% (95% CI 82 to 95); negative LR 0.22 (95% CI 0.13 to 0.38) versus 0.49 (95% CI 0.35 to 0.66); and positive LR 5.2 (95% CI 3.2 to 8.6) versus 5.6 (95% CI 2.9 to 11). CONCLUSION: For the diagnosis of occlusion myocardial infarction in the presence of ventricular paced rhythm, the MSC were more sensitive than the original Sgarbossa criteria; specificity was high for both rules. The MSC may contribute to clinical decisionmaking for patients with ventricular paced rhythm.

Seed treatment with prodigiosin controls damping-off of cucumber caused by Pythium ultimum.

Ethanol extract of cell mass of Serratia marcescens strain N4-5, when applied as a treatment to cucumber seed, has been shown to provide control of the oomycete soil-borne plant pathogen Pythium ultimum equivalent to that provided by a seed-treatment chemical pesticide in some soils. Two dominant compounds in this extract, prodigiosin and the serratamolide serrawetin W1, were identified based on mass and collision induced dissociation mass fragmentation spectra. An additional four compounds with M+H+ masses (487, 541, 543, and 571) consistent with serratamolides reported in the literature were also detected. Several other compounds with M+H+ masses of 488, 536, 684, 834, 906, and 908 m/z were detected in this ethanol extract inconsistently over multiple liquid chromatography coupled with tandem mass spectrometry (LC/MS-MS) runs. A purified preparation of prodigiosin provided control of damping-off of cucumber caused by P. ultimum when applied as a seed treatment while ethanol extract of cell mass of strain Tn246, a transposon-mutant-derivative of strain N4-5, did not. Strain Tn246 contained a mini-Tn5 Km insertion in a prodigiosin biosynthetic gene and was deficient in production of prodigiosin. All other compounds detected in N4-5 extract were detected in the Tn246 extract. This is the first report demonstrating that prodigiosin can control a plant disease. Other compounds in ethanol extract of strain N4-5 may contribute to disease control.

Fluxes of agricultural nitrogen and metolachlor metabolites are highly correlated in a first order stream in Maryland, USA.

Nitrogen pollution in watersheds containing significant cropland area is generally problematic. Conservation practices intended to reduce nitrate-N (NO3--N) export from watersheds are being implemented by many regions without necessary tools to assess effectiveness of abatement. A commonly used herbicide metolachlor degrades in the vadose zone of croplands to form two metabolites (metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA)) which are both highly soluble in soils. Study of metabolite fates in a first order watershed provided evidence that transport of these metabolites to stream water is highly correlated to transport of agricultural NO3--N that also forms in the cropland vadose zone. Linear models describing the relationships of stream flux of MESA and MOXA to NO3--N flux generated goodness of fit values of 0.93 and 0.81, respectively. These findings support a conclusion that both MESA and MOXA act as excellent transport analogs of NO3--N and become strongly correlated to agricultural NO3--N leaching from the cropland vadose zone. Moreover, their use as conservative tracers in agricultural watersheds can provide valuable information concerning movement and fate of agricultural nitrogen at watershed scales of observation.

Method to Evaluate the Age of Groundwater Inputs to Surface Waters by Determining the Chirality Change of Metolachlor Ethanesulfonic Acid (MESA) Captured on a Polar Organic Chemical Integrative Sampler (POCIS).

We previously discovered a method to estimate the groundwater mean residence time using the changes in the enantiomeric ratio of metolachlor ethanesulfonic acid (MESA), (2-[(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid), a metabolite of the herbicide metolachlor. However, many grab samples would be needed for each watershed over an extended period, and this is not practical. Thus, we examined the use of a polar organic chemical integrative sampler (POCIS) deployed for 28 days combined with a modified liquid chromatography-mass spectrometry LC-MS/MS method to provide a time-weighted average of the MESA enantiomeric ratio. POCISs equipped with hydrophilic-lipophilic-balanced (HLB) discs were deployed at five sites across the United States where metolachlor was used before and after 1999 and compared the effectiveness of the POCIS to capture MESA versus grab samples. In addition, an in situ POCIS sampling rate (Rs) for MESA was calculated (0.15 L/day), the precision of MESA extraction from stored POCIS discs was determined, and the effectiveness of HLB to extract MESA was examined. Finally, using molecular modeling, the influence of the asymmetric carbon of metolachlor degradation on the MESA enantiomeric ratio was predicted to be negligible. Results of this work will be used in projects to discern the groundwater mean residence times, to evaluate the delivery of nitrate-N from groundwater to surface waters under various soil, agronomic, and land use conditions, and to examine the effectiveness of conservation practices.

Resident Supervision and Patient Care: A Comparative Time Study in a Community-Academic Versus a Community Emergency Department.

OBJECTIVE: The objective was to compare attending emergency physician (EP) time spent on direct and indirect patient care activities in emergency departments (EDs) with and without emergency medicine (EM) residents. METHODS: We performed an observational, time-motion study on 25 EPs who worked in a community-academic ED and a nonacademic community ED. Two observations of each EP were performed at each site. Average time spent per 240-minute observation on main-category activities are illustrated in percentages. We report descriptive statistics (median and interquartile ranges) for the number of minutes EPs spent per subcategory activity, in total and per patient. We performed a Wilcoxon two-sample test to assess differences between time spent across two EDs. RESULTS: The 25 observed EPs executed 34,358 tasks in the two EDs. At the community-academic ED, EPs spent 14.2% of their time supervising EM residents. Supervision activities included data presentation, medical decision making, and treatment. The time spent on supervision was offset by a decrease in time spent by EPs on indirect patient care (specifically communication and electronic health record work) at the community academic ED compared to the nonacademic community ED. There was no statistical difference with respect to direct patient care time expenditure between the two EDs. There was a nonstatistically significant difference in attending patient load between sites. CONCLUSIONS: EPs in our study spent 14.2% of their time (8.5 minutes/hour) supervising residents. The time spent supervising residents was largely offset by time savings related to indirect patient care activities rather than compromising direct patient care.

Insights into the metabolism and behaviour of Varroa destructor mites from analysis of their waste excretions.

Varroa destructor mites (Acari: Varroidae) are harmful ectoparasites of Apis mellifera honey bees. Female foundresses of wax-capped pupal host cells and their daughters feed on host fluids from open wounds on the host's integument. Details of V. destructor mite nutrition are forthcoming, and little is known about the potential physical effects on hosts from mite feeding. Chemical analysis of waste excretions can infer details of animals' nutrition. Here, chemical analysis by high-performance liquid chromatography/mass spectrometry (HPLC-MS/MS) of mite excretions showed that the purine content of V. destructor waste consists of guanine with traces of hypoxanthine. Traces of uric acid and caffeine were also detected. Concentrations of guanine attenuated over time and excretions collected from senescing mites did not contain detectable guanine. Non-reproducing individual female mites maintained in vitro, housed in gelatin capsules and provided a honey bee pupa, deposited an average of nearly 18 excretions daily, mostly on the host's integument rather than on the capsule wall. The weight and volume of excretions suggest mites can consume nearly a microlitre of host fluids each day. Compounded over 10 days, this together with open wounds, could lead to substantial water loss and stress to developing pupae.

Fate of four phthalate plasticizers under various wastewater treatment processes.

The fate of four phthalate plasticizers during wastewater treatment processes at six different wastewater treatment plants (WWTPs) was investigated. Concentrations of benzyl butyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DiNP), and diisodecyl phthalate (DiDP) were determined prior to either aerobic or anaerobic (conventional and advanced) treatment, after treatment, and in final, dewatered solids. Despite their elevated use worldwide, the fate of DiNP and DiDP during wastewater treatment have not been well characterized. DEHP was readily degraded during aerobic treatments while anaerobic digestion resulted in either no significant change in concentrations or an increase in concentration, in the case of more advanced anaerobic processes (thermal hydrolysis pretreatment and a two-phase acid/gas process). Impacts of the various treatment systems on DiNP, DiDP, and BBP concentrations were more varied - anaerobic digestion led to significant decreases, increases, or no significant change for these compounds, depending on the treatment facility, while aerobic treatment was generally effective at degrading the compounds. Additionally, thermal hydrolysis pretreatment of sludge prior to anaerobic digestion resulted in increases in DiNP, DiDP, and BBP concentrations. The predicted environmental concentrations for all four compounds in soils after a single biosolids application were calculated and the risk quotients for DEHP in soils were determined. The estimated toxicity risk for DEHP in soils treated with a single application of sludge from any of the six studied WWTPs is lower than the level of concern for acute and chronic risk, as defined by the US EPA.

The fate and effect of monensin during anaerobic digestion of dairy manure under mesophilic conditions.

There is growing concern about residual antibiotics and feed additives in the manure of treated animals because of the effects of these residues in the environment. Monensin is the most widely used ionophore coccidiostat in the U.S. The objective of this study was to determine the fate and effect of monensin during the anaerobic digestion of dairy manure. Duplicate plug flow field-scale digesters were operated using non-amended dairy manure and dairy manure amended with monensin to 1 and 10 mg/L for 56 days at 30°C at an organic loading rate of 1.4 kg VS/m3-d and 17-day hydraulic retention time. Results showed that monensin was reduced approximately 70% during anaerobic digestion. Methane production from digesters using manure amended with 1 mg/L monensin was comparable to that from digesters operated without added monensin. However, digesters using manure amended with 10 mg/L monensin yielded 75% less methane than digesters using manure without added monensin. These results suggest that anaerobic digestion is an effective treatment for reducing, but not eliminating, monensin in dairy manure. Monensin did not reduce methane production at concentrations expected in dairy manure at recommended dosage rates.

Degradation of triclosan and triclocarban and formation of transformation products in activated sludge using benchtop bioreactors.

Benchtop bioreactors were run aerobically with activated sludge samples collected from a large municipal wastewater treatment plant (WWTP) to understand how increased hydraulic retention time (HRT), sludge retention time (SRT), and varying treatment temperatures (21°C and 30°C) impact concentrations of the endocrine disrupting antimicrobials triclosan (TCS), triclocarban (TCC), and their transformation products. Samples from the reactors were collected periodically over a 122-196h period and the solid and liquid fraction were separately quantitated for TCS, TCC, and methyltriclosan (MeTCS) and scanned qualitatively for six other transformation products. Results indicated that TCS, TCC and MeTCS were predominately associated with the solids fraction of the activated sludge with only nominal concentrations in the liquids fraction. TCS was degraded in the solids fraction, with increased rates at 30°C (-0.0224 ± 0.007h-1) when compared to reactors run at 21°C (- 0.0170 ± 0.003h-1). Conversely, TCC concentrations did not significantly change in solids samples from reactors run at 21°C, while an increase in reactor temperature to 30°C resulted in TCC degradation at an average rate of - 0.0158 ± 0.012h-1. Additionally, MeTCS formation in the solids fraction was observed in three out of four reactors run - indicating a notable transformation of TCS. Qualitative appearance of 2,4-dichlorophenol and 4-chloroanaline was observed in the liquids fraction of all reactor samples. The remaining four qualitatively scanned compounds were not detected. These experiments demonstrate that increased HRT, SRT, and temperature result in enhanced removal of TCS and TCC from wastewater during the activated sludge process. Furthermore, a substantial formation of TCS into MeTCS was observed.

Fate of triclocarban in agricultural soils after biosolid applications.

Triclocarban [N-(4-chlorophenyl)-N-(3,4-dichlorophenyl) urea] (TCC) is an antimicrobial agent utilized in a variety of consumer products. It is commonly released into domestic wastewaters and upon treatment, it is known to accumulate in biosolids. This study examines the occurrence of TCC in biosolids and its long-term fate in biosolid-treated soils. TCC levels in the biosolids from a large waste water treatment plant (WWTP) over 2 years showed little variability at 18,800 ± 700 ng g-1 dry wt. (mean ± SEM). Surface soil samples (top 10 cm) were collected from 26 commercial farms located in northern VA, US that had received biosolid applications from the WWTP. Samples were grouped as farms receiving no biosolids, farms with a single biosolid application, and those receiving multiple biosolid applications from 1992 to 2006. Our results illustrate that TCC soil residues remained years after biosolid application. The two most important parameters controlling TCC topsoil concentrations were the biosolid application rate and the period since the last application. No TCC removal was observed in farms where the time since biosolid application was between 7 and 9 months. TCC concentration analyzed 7 and 8 years after biosolid applications were 45.8 ± 6.1 and 72.4 ± 15.3 ng g-1 dry wt., respectively, showing its persistence in soils and build-up upon multiple biosolid applications. A soil TCC half-life of 287.5 ± 45.5 days was estimated.

Influence of thermal hydrolysis-anaerobic digestion treatment of wastewater solids on concentrations of triclosan, triclocarban, and their transformation products in biosolids.

The growing concern worldwide regarding the presence of emerging contaminants in biosolids calls for a better understanding of how different treatment technologies at water resource recovery facilities (WRRFs) can influence concentrations prior to biosolids land application. This study focuses on the influence of solids treatment via the Cambi Thermal Hydrolysis Process™ in conjunction with anaerobic digestion (TH-AD) on concentrations of triclosan (TCS), triclocarban (TCC), and their transformation products in biosolids and sludges. Concentrations of the target analytes in biosolids from the TH-AD process (Class A), sludges from the individual TH-AD treatment steps, and limed biosolids (Class B) from the same WRRF were compared. TCC concentrations were significantly lower in Class A biosolids than those in the Class B product - a removal that occurred during thermal hydrolysis. Concentrations of TCS, methyl triclosan, and 2,4-dichlorophenol, conversely, increased during anaerobic digestion, leading to significantly higher concentrations of these compounds in Class A biosolids when compared to Class B biosolids. Implementation of the TH-AD process had mixed effect on contaminant concentrations.

The effect of composting on the persistence of four ionophores in dairy manure and poultry litter.

Manure composting is a well-described approach for stabilization of nutrients and reduction of pathogens and odors. Although composting studies have shown that thermophilic temperatures and aerobic conditions can increase removal rates of selected antibiotics, comparable information is lacking for many other compounds in untreated or composted manure. The objective of this study was to determine the relative effectiveness of composting conditions to reduce concentrations of four widely used ionophore feed supplements in dairy manure and poultry litter. Replicate aliquots of fresh poultry litter and dairy manure were amended with monensin, lasalocid, salinomycin, or amprolium to 10mgkg(-1)DW. Non-amended and amended dairy manure and poultry litter aliquots were incubated at 22, 45, 55, or 65°C under moist, aerobic conditions. Residue concentrations were determined from aliquots removed after 1, 2, 4, 6, 8, and 12weeks. Results suggest that the effectiveness of composting for contaminant reduction is compound and matrix specific. Composting temperatures were not any more effective than ambient temperature in increasing the rate or extent of monensin removal in either poultry litter or dairy manure. Composting was effective for lasalocid removal in poultry litter, but is likely to be too slow to be useful in practice (8-12weeks at 65°C for >90% residue removal). Composting was effective for amprolium removal from poultry litter and salinomycin in dairy manure but both required 4-6weeks for >90% removal. However, composting did not increase the removal rates or salinomycin in poultry litter or the removal rates of lasalocid or amprolium in dairy manure.

Analysis of metolachlor ethane sulfonic acid (MESA) chirality in groundwater: A tool for dating groundwater movement in agricultural settings.

UNLABELLED: To better address how much groundwater contributes to the loadings of pollutants from agriculture we developed a specific dating tool for groundwater residence times. This tool is based on metolachlor ethane sulfonic acid, which is a major soil metabolite of metolachlor. The chiral forms of metolachlor ethane sulfonic acid (MESA) and the chiral forms of metolachlor were examined over a 6-year period in samples of groundwater and water from a groundwater-fed stream in a riparian buffer zone. This buffer zone bordered cropland receiving annual treatments with metolachlor. Racemic (rac) metolachlor was applied for two years in the neighboring field, and subsequently S-metolachlor was used which is enriched by 88% with the S-enantiomer. Chiral analyses of the samples showed an exponential increase in abundance of the S-enantiomeric forms for MESA as a function of time for both the first order riparian buffer stream (R(2)=0.80) and for groundwater within the riparian buffer (R(2)=0.96). However, the S-enrichment values for metolachlor were consistently high indicating different delivery mechanisms for MESA and metolachlor. A mean residence time of 3.8years was determined for depletion of the initially-applied rac-metolachlor. This approach could be useful in dating groundwater and determining the effectiveness of conservation measures. ONE SENTENCE SUMMARY: A mean residence time of 3.8years was calculated for groundwater feeding a first-order stream by plotting the timed-decay for the R-enantiomer of metolachlor ethane sulfonic acid.

Isolation and identification of nematode-antagonistic compounds from the fungus Aspergillus candidus.

Culture medium from an isolate of the fungus Aspergillus candidus was extracted, fractionated and examined to discover compounds antagonistic to plant-parasitic nematodes that are important pathogens of agricultural crops. Column, thin layer and preparative chromatographies and spectral and elemental analyses, were used to isolate and identify two major constituents of an active fraction (Fraction F) obtained from the medium. Compound 1 was identified as 2-hydroxypropane-1, 2, 3-tricarboxylic acid (citric acid). Compound 2 was identified as 3-hydroxy-5-methoxy-3-(methoxycarbonyl)-5-oxopentanoic acid, an isomer of 1, 2-dimethyl citrate. Compound 1 and a citric acid standard, each tested at 50 mg mL(-1) in water, decreased hatch from eggs of the plant-parasitic nematode Meloidogyne incognita by more than 94%, and completely immobilized second-stage juveniles after 4-6 days exposure. Fraction F and Compounds 1 and 2 decreased the mobility of adults of the plant-parasitic nematode Ditylenchus destructor in vitro. Fraction F (25 mg mL(-1)) inhibited mobility >99% at 72 hrs. Compounds 1 and 2 (50 mg mL(-1)) each inhibited mobility more than 25% at 24 hr and more than 50% at 72 hr. This is the first assignment of nematode-antagonistic properties to specifically identified A. candidus metabolites.

Temporal trends of perfluoroalkyl substances in limed biosolids from a large municipal water resource recovery facility.

While the recycling of wastewater biosolids via land-application is a sustainable practice for nutrient recovery and soil reclamation that has become increasingly common worldwide, concerns remain that this practice may become a source of toxic, persistent organic pollutants to the environment. This study concentrates on assessing the presence and the temporal trends of 12 perfluoroalkyl substances (PFASs), pollutants of global consequence, in limed Class B biosolids from a municipal water resource recovery facility (WRRF), also know as a wastewater treatment plant. PFASs are of significant concern due to their extensive presence and persistence in environmental and biotic samples worldwide, most notably human blood samples. Class B biosolids were collected from the WRRF, prior to land-application, approximately every two to three months, from 2005 to 2013. Overall, this study found that concentrations of the 7 detectable PFAS compounds remained unchanged over the 8-year period, a result that is consistent with other temporal studies of these compounds in sewage sludges. From these analyzed compounds, the highest mean concentrations observed over the study period were 25.1 ng/g dw, 23.5 ng/g dw, and 22.5 ng/g dw for perfluorononanoic acid (PFNA), perfluorooctanoic acid (PFOA), and perfluorooctanesulfonic acid (PFOS), respectively, and these compounds were detected at concentrations 2.5-5 times higher than the remaining, detectable PFASs. Furthermore, it was observed that PFOS, while demonstrating no overall change during the study, exhibited a visible spike in concentration from late 2006 to early 2007. This study indicates that concentrations of PFASs in WRRFs have been stagnant over time, despite regulation. This study also demonstrates that the use of glass jars with polytetrafluoroethylene-lined lids, a common storage method for environmental samples, will not influence PFOA and PFNA concentrations in archived biosolids samples.

Endocrine disrupting alkylphenolic chemicals and other contaminants in wastewater treatment plant effluents, urban streams, and fish in the Great Lakes and Upper Mississippi River Regions.

Urban streams are an integral part of the municipal water cycle and provide a point of discharge for wastewater treatment plant (WWTP) effluents, allowing additional attenuation through dilution and transformation processes, as well as a conduit for transporting contaminants to downstream water supplies. Domestic and commercial activities dispose of wastes down-the-drain, resulting in wastewater containing complex chemical mixtures that are only partially removed during treatment. A key issue associated with WWTP effluent discharge into streams is the potential to cause endocrine disruption in fish. This study provides a long-term (1999-2009) evaluation of the occurrence of alkylphenolic endocrine disrupting chemicals (EDCs) and other contaminants discharged from WWTPs into streams in the Great Lakes and Upper Mississippi River Regions (Indiana, Illinois, Michigan, Minnesota, and Ohio). The Greater Metropolitan Chicago Area Waterways, Illinois, were evaluated to determine contaminant concentrations in the major WWTP effluents and receiving streams, and assess the behavior of EDCs from their sources within the sewer collection system, through the major treatment unit processes at a WWTP, to their persistence and transport in the receiving stream. Water samples were analyzed for alkylphenolic EDCs and other contaminants, including 4-nonylphenol (NP), 4-nonylphenolpolyethoxylates (NPEO), 4-nonylphenolethoxycarboxylic acids (NPEC), 4-tert-octylphenol (OP), 4-tert-octylphenolpolyethoxylates (OPEO), bisphenol A, triclosan, ethylenediaminetetraacetic acid (EDTA), and trace elements. All of the compounds were detected in all of the WWTP effluents, with EDTA and NPEC having the greatest concentrations. The compounds also were detected in the WWTP effluent dominated rivers. Multiple fish species were collected from river and lake sites and analyzed for NP, NPEO, NPEC, OP, and OPEO. Whole-body fish tissue analysis indicated widespread occurrence of alkylphenolic compounds, with the highest concentrations occurring in streams with the greatest WWTP effluent content. Biomarkers of endocrine disruption in the fish indicated long-term exposure to estrogenic chemicals in the wastewater impacted urban waterways.