Occurrence, temporal variation, and estrogenic burden of five parabens in sewage sludge collected across the United States.
ABSTRACT: Five parabens used as preservatives in pharmaceuticals and personal care products (PPCPs) were measured in sewage sludges collected at 14 U.S. wastewater treatment plants (WWTPs) located in nine states. Detected concentration ranges (ng/g, dry weight) and frequencies were as follows: methyl paraben (15.9 to 203.0; 100%), propyl paraben (0.5 to 7.7; 100%), ethyl paraben (<0.6 to 2.6; 63%), butyl paraben (<0.4 to 4.3; 42%) and benzyl paraben (<0.4 to 3.3; 26%). The estrogenicity inherent to the sum of parabens detected in sewage sludge (ranging from 10.1 to 500.1pg/kg 17?-estradiol equivalents) was insignificant when compared to the 106-times higher value calculated for natural estrogens reported in the literature to occur in sewage sludge. Temporal monitoring at one WWTP provided insights into temporal and seasonal variations in paraben concentrations. This is the first report on the occurrence of five parabens in sewage sludges from across the U.S., and internationally, the first on temporal variations of paraben levels in sewage sludge. Study results will help to inform the risk assessment of sewage sludge destined for land application (biosolids).
Project description:The objective of the study was to determine the leachates toxicity from sewage sludge-amended soils (sandy and loamy). Samples originated from a plot experiment realized over a period of 29 months. Two types of soil were fertilized with sewage sludges at the dose of 3 % (90 t/ha). Soil samples were taken after 0, 7, 17, and 29 months from the application of sewage sludges. Leachates were obtained according to the EN 12457-2 protocol. The following commercial tests were applied for the estimation of the toxicity: Microtox (Vibrio fischeri), Microbial assay for toxic risk assessment (ten bacteria and one yeast), Protoxkit F (Tetrahymena thermophila), Rotoxkit F (Brachionus calyciflorus), and Daphtoxkit F (Daphnia magna). The test organisms displayed varied toxicity with relation to the soils amended with sewage sludges. The toxicity of the leachates depended both on the soil type and on the kind of sewage sludge applied. Notable differences were also observed in the sensitivity of the test organisms to the presence of sewage sludge in the soil. The highest sensitivity was a characteristic of B. calyciflorus, while the lowest sensitivity to the presence of the sludges was revealed by the protozoa T. thermophila. Throughout the periods of the study, constant variations of toxicity were observed for most of the test organisms. The intensity as well as the range of those variations depended both on the kind of test organism and on the kind of sludge and soil type. In most cases, an increase of the toxicity of soils amended with the sewage sludges was observed after 29 months of the experiment.
Project description:In response to the U.S. National Academies' call for a better assessment of chemical pollutants contained in the approximately 7 million dry tons of digested municipal sludge produced annually in the United States, the mean concentration of 72 pharmaceuticals and personal care products (PPCP) were determined in 110 biosolids samples collected by the U.S. Environmental Protection Agency (EPA) in its 2001 National Sewage Sludge Survey. Composite samples of archived biosolids, collected at 94 U.S. wastewater treatment plants from 32 states and the District of Columbia, were analyzed by liquid chromatography tandem mass spectrometry using EPA Method 1694. Thirty-eight (54%) of the 72 analytes were detected in at least one composite sample at concentrations ranging from 0.002 to 48 mg kg(-1) dry weight. Triclocarban and triclosan were the most abundant analytes with mean concentrations of 36 +/- 8 and 12.6 +/- 3.8 mg kg(-1) (n = 5), respectively, accounting for 65% of the total PPCP mass found. The loading to U.S. soils from nationwide biosolids recycling was estimated at 210-250 metric tons per year for the sum of the 72 PPCPs investigated. The results of this nationwide reconnaissance of PPCPs in archived U.S. biosolids mirror in contaminant occurrences, frequencies and concentrations, those reported by the U.S. EPA for samples collected in 2006/2007. This demonstrates that PPCP releases in U.S. biosolids have been ongoing for many years and the most abundant PPCPs appear to show limited fluctuations in mass over time when assessed on a nationwide basis. The here demonstrated use of five mega composite samples holds promise for conducting cost-effective, routine monitoring on a regional and national basis.
Project description:The insecticide fipronil is under regulatory scrutiny worldwide for its toxicity to pollinators and aquatic invertebrates. We conducted the first U.S. nationwide, longitudinal study of sewage sludges for fiproles, i.e., the sum of fipronil and its major degradates (fipronil sulfone, sulfide, amide, and desulfinyl). Archived sludges (n?=?109) collected in three campaigns over 15 years were analyzed by isotope dilution liquid chromatography tandem mass spectrometry, revealing ubiquitous fiprole occurrence (0.2-385.3??g/kg) since 2001 and a significant increase (2.4?±?0.3 fold; p?<?0.005) both from 2001 to 2006/7 and from 2001 to 2015/6, but not a significant increase from 2006/7 to 2015/6 (p?=?0.275). A geospatial analysis showed fiprole levels in municipal sludges to be uncoupled from agricultural use of fipronil on cropland surrounding sampled municipalities, thus pointing to non-agricultural uses (i.e., spot-on treatment and urban pest control) as a major source of fiprole loading to wastewater. Whereas anaerobic digestion was correlated with increases in fipronil sulfide at the expense of parental fipronil (p?<?0.001), total fiprole levels in sewage sludges were similar regardless of the solids treatment approach applied (p?=?0.519). Treatment plant effluent available from 12 facilities in 2015/6 contained fiproles at 0.3-112.9?ng/L, exceeding the United States Environmental Protection Agency (USEPA) aquatic invertebrate life benchmark for chronic fipronil exposure (11?ng/L) in 67% of cases. Whereas the USEPA identified fipronil in sludge only recently (2015), retrospective analyses and modeling conducted here show contaminant ubiquity and nationwide increases of fiprole mass (compared to 2001 levels) in U.S. municipal sludge (1140?±?230?kg in 2015/6), and treated effluent nationwide (1970?±?390?kg in 2015/6) over the past 15 years.
Project description:BACKGROUND:Emerging experimental studies suggest that parabens could affect metabolism by altering the microbiome or signaling pathways involved in adipocyte differentiation. While human exposure to parabens is widespread, epidemiologic studies assessing the role of these chemicals on adiposity measures are scarce. OBJECTIVE:We examined associations of parabens with adiposity measures among adults and children in the U.S. general population. METHODS:We conducted covariate-adjusted linear and logistic regression models to examine associations between urinary biomarker concentrations of four parabens (butyl-BP, ethyl-EP, methyl-MP, and propyl paraben-PP) and measures of adiposity (obesity; body mass index, BMI or BMI z-score; and waist circumference) among 4730 adults (2007-2014) and 1324 children (2007-2012), participating in the National Health and Nutrition Examination Survey. We also assessed heterogeneity of associations by gender. RESULTS:We generally observed significant inverse associations between adiposity measures and paraben biomarker concentrations among adults (BP, EP, MP, PP) and children (MP). For example, adjusted prevalence odds ratios (95% confidence intervals, CI) for obesity per a ten-fold increase in MP concentrations were 0.64 (95% CI: 0.55, 0.73) for adults and 0.71(95% CI: 0.52, 0.95) for children. Strength of inverse associations typically increased monotonically with increasing paraben exposure quartiles; and, in general, inverse associations were more pronounced among females. Associations remained when controlling for other phenolic compounds previously linked with adiposity measures. CONCLUSIONS:In this cross-sectional study of adiposity measures and parabens, we observed consistent inverse associations in a representative sample of U.S adults and children. Further studies are warranted to confirm our findings, examine the potential role of paraben sequestration in adipose tissue, and elucidate mechanisms by which parabens could alter metabolism.
Project description:In the present study, archived U.S biosolids from the 2001 Environmental Protection Agency (EPA) National Sewage Sludge Survey were analyzed with an expanded U.S EPA Method 1694, to determine the occurrence of 26 previously unmonitored pharmaceuticals and personal care products (PPCPs) among a total of 120 analytes. The study further served to examine the reproducibility of a mega-composite approach for creating chemical mass inventories in biosolids based on pooled samples from wastewater treatment plants (WWTPs) nationwide. Five mega-composites reflecting 94 WWTPs in 32 states and the District of Columbia were constructed from archived biosolids and analyzed by LC/ESI-MS/MS using a newly introduced analytical method expanding upon U.S EPA Method 1694. In addition, soil-biosolids mixtures from a mesocosm setup were analyzed to experimentally determine the half-lives of biosolids-borne compounds applied on U.S land. Among 59 analytes detected, 33 had been reported previously, whereas 26 are reported in biosolids for the first time, at levels ranging from 1.65 to 673 ?g kg?¹ dry weight. Newly recognized biosolids constituents were identified as Ca²? channel blockers, antidepressants, diuretics, ?-blockers and analgesics. Using a mass balance approach, the total loading of these 26 pharmaceuticals to U.S soils from biosolids land application was estimated at 5-15 tons year?¹. Past and present datasets for 30 pharmaceuticals and personal care products (PPCPs) were determined to be statistically indistinguishable (paired t-test; p = 0.01). This study expands the list of PPCPs reported in U.S biosolids, provides the first estimates of nationwide release rates to and environmental half-lives in U.S agricultural soils, and confirms the utility of using mega-composite sampling for economical tracking of chemical inventories in biosolids on a national scale.
Project description:Sewage sludges generation and their disposal have become one of the greatest challenges of the 21st century. They have great microbial diversity that may impact wastewater treatment plant (WWTP) efficiency and soil quality whether used as fertilizers. Therefore, this research aimed to characterize microbial community diversity and structure of 19 sewage sludges from São Paulo, Brazil, as well as to draw their relations to sludge sources [domestic and mixed (domestic+industrial)], biological treatments (redox conditions and liming), and chemical attributes, using molecular biology as a tool. All sludges revealed high bacterial diversity, but their sources and redox operating conditions as well as liming did not consistently affect bacterial community structures. Proteobacteria was the dominant phylum followed by Bacteroidetes and Firmicutes; whereas Clostridium was the dominant genus followed by Treponema, Propionibacterium, Syntrophus, and Desulfobulbus. The sludge samples could be clustered into six groups (C1 to C6) according their microbial structure similarities. Very high pH (?11.9) was the main sludge attribute segregating C6, that presented very distinct microbial structure from the others. Its most dominant genera were Propionibacterium > > Comamonas > Brevundimonas > Methylobacterium ?Stenotrophomonas ?Cloacibacterium. The other clusters' dominant genera were Clostridium > > Treponema > Desulfobulbus ?Syntrophus. Moreover, high Fe and S were important modulators of microbial structure in certain sludges undertaking anaerobic treatment and having relatively low N-Kj, B, and P contents (C5). However, high N-Kj, B, P, and low Fe and Al contents were typical of domestic, unlimed, and aerobically treated sludges (C1). In general, heavy metals had little impact on microbial community structure of the sludges. However, our sludges shared a common core of 77 bacteria, mostly Clostridium, Treponema, Syntrophus, and Comamonas. They should dictate microbial functioning within WWTPs, except by SS12 and SS13.
Project description:The distribution and phylogenetic affiliations of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)-degrading denitrifying bacteria in activated sludge were studied by a polyphasic approach including culture-independent biomarker and molecular analyses as well as cultivation methods. A total of 23 strains of PHBV-degrading denitrifiers were isolated from activated sludges from different sewage treatment plants. 16S ribosomal DNA (rDNA) sequence comparisons showed that 20 of the isolates were identified as members of the family Comamonadaceae, a major group of beta-Proteobacteria. When the sludges from different plants were acclimated with PHBV under denitrifying conditions in laboratory scale reactors, the nitrate removal rate increased linearly during the first 4 weeks and reached 20 mg NO(3)(-)-N h(-1) g of dry sludge(-1) at the steady state. The bacterial-community change in the laboratory scale sludges during the acclimation was monitored by rRNA-targeted fluorescence in situ hybridization and quinone profiling. Both approaches showed that the population of beta-Proteobacteria in the laboratory sludges increased sharply during acclimation regardless of their origins. 16S rDNA clone libraries were constructed from two different acclimated sludges, and a total of 37 clones from the libraries were phylogenetically analyzed. Most of the 16S rDNA clones were grouped with members of the family Comamonadaceae. The results of our polyphasic approach indicate that beta-Proteobacteria, especially members of the family Comamonadaceae, are primary PHBV-degrading denitrifiers in activated sludge. Our data provide useful information for the development of a new nitrogen removal system with solid biopolymer as an electron donor.
Project description:The aim of the present study was the estimation of changes in the phytotoxicity of soils amended with sewage sludge with relation to Lepidium sativum, Sinapis alba and Sorghum saccharatum. The study was realised in the system of a plot experiment for a period of 29 months. Samples for analyses were taken at the beginning of the experiment, and then after 5, 17 and 29 months. Two kinds of sewage sludge, with varying properties, were added to a sandy soil (soil S) or a loamy soil (soil L) at the dose of 90 t/ha. The addition of sewage sludge to the soils at the start of the experiment caused a significant reduction of both seed germination capacity and root length of the test plants, the toxic effect being distinctly related to the test plant species. With the passage of time the negative effect of sewage sludge weakened, the extent of its reduction depending both of the kind of sewage sludge applied and on the type of soil. Phytotoxicity of the soils amended with the sewage sludges was significantly lower at the end of the experiment than at the beginning. The species of the plants grown on the soils also had a significant effect on their phytotoxicity. The greatest reduction of toxicity was observed in the soil on which no plants were grown (sandy soil) and in the soil under a culture of willow (loamy soil). Solid phase of sewage sludge-amended soils was characterised by higher toxicity than their extracts. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s11270-012-1248-8) contains supplementary material, which is available to authorized users.
Project description:This article presents the outcomes of higher-tier repeated-dose toxicity studies and developmental and reproductive toxicity (DART) studies using Wistar rats requested for methyl paraben and propyl paraben under the European Union chemicals legislation. All studies revealed no-observed adverse effects (NOAELs) at 1000 mg/kg body weight/day. These findings (absence of effects) were then used to interpolate the hazard profile for ethyl paraben, further considering available data for butyl paraben. The underlying read-across hypothesis (all shorter-chained linear n-alkyl parabens are a 'category' based on very high structural similarity and are transformed to a common compound) was confirmed by similarity calculations and comparative in vivo toxicokinetics screening studies for methyl paraben, ethyl paraben, propyl paraben and butyl paraben. All four parabens were rapidly taken up systemically following oral gavage administration to rats, metabolised to p-hydroxybenzoic acid, and rapidly eliminated (parabens within one hour; p-hydroxybenzoic acid within 4-8 h). Accordingly, for ethyl paraben, the NOAELs for repeated-dose toxicity and DART were interpolated to be 1000 mg/kg body weight/day. Finally, all evidence was evaluated to address concerns expressed in the literature that parabens might be endocrine disruptors. This evaluation showed that the higher-tier studies do not provide any indication for any endocrine disrupting property. This is the first time that a comprehensive dataset from higher-tier in vivo studies following internationally agreed test protocols has become available for shorter-chained linear n-alkyl parabens. Consistently, the dataset shows that these parabens are devoid of repeated-dose toxicity and do not possess any DART or endocrine disrupting properties.
Project description:Triclosan and parabens are chemicals used in personal care and medical products as microbicides and preservatives. Triclosan and paraben exposure may be associated with allergy (atopy), but these associations have not been evaluated with respect to other atopic states such as eczema (atopic dermatitis). This study examines the associations of urinary triclosan and paraben concentrations with allergic sensitization and asthma in children according to eczema history. We performed a cross-sectional analysis of U.S. children aged 6-18 years who participated in the National Health and Nutrition Examination Survey (2005-2006). Triclosan and paraben concentrations were measured in urine. We assessed associations of triclosan and parabens with allergic sensitization and asthma using multivariable logistic regression in 837 children with complete data and stratified our results by eczema status. After covariate adjustment, triclosan and methyl and propyl paraben concentrations were positively associated with the odds of aeroallergen sensitization. Eczema did not significantly modify the association between triclosan or paraben levels and aeroallergen sensitization, asthma, or wheeze. The odds of parent-reported atopic asthma increased 34% (95% CI, 0, 81) across triclosan concentration quartiles. Increasing triclosan concentrations (quartiles) were associated with 2.3 times the odds of food sensitization (95% CI, 1.14, 4.44) among children with eczema, but not among children without eczema (OR, 1.25; 95% CI 0.93, 1.68; effect measure modification, p = 0.04). Triclosan and paraben exposures may increase the risk of atopic asthma and aeroallergen sensitization. Prospective studies are necessary to confirm these findings and determine if these chemicals pose a risk to children's health.