Logistic Regression Analysis of LC-MS/MS Data of Monomers Eluted from Aged Dental Composites: A Supervised Machine-Learning Approach.

Compound identification by database searching that matches experimental with library mass spectra is commonly used in mass spectrometric (MS) data analysis. Vendor software often outputs scores that represent the quality of each spectral match for the identified compounds. However, software-generated identification results can differ drastically depending on the initial search parameters. Machine learning is applied here to provide a statistical evaluation of software-generated compound identification results from experimental tandem MS data. This task was accomplished using the logistic regression algorithm to assign an identification probability value to each identified compound. Logistic regression is usually used for classification, but here it is used to generate identification probabilities without setting a threshold for classification. Liquid chromatography coupled with quadrupole-time-of-flight tandem MS was used to analyze the organic monomers leached from resin-based dental composites in a simulated oral environment. The collected tandem MS data were processed with vendor software, followed by statistical evaluation of these results using logistic regression. The assigned identification probability to each compound provides more confidence in identification beyond solely by database matching. A total of 21 distinct monomers were identified among all samples, including five intact monomers and chemical degradation products of bisphenol A glycidyl methacrylate (BisGMA), oligomers of bisphenol-A ethoxylate methacrylate (BisEMA), triethylene glycol dimethacrylate (TEGDMA), and urethane dimethacrylate (UDMA). The logistic regression model can be used to evaluate any database-matched liquid chromatography-tandem MS result by training a new model using analytical standards of compounds present in a chosen database and then generating identification probabilities for candidates from unknown data using the new model.

Spatial and Temporal Trends of Polyhalogenated Carbazoles in Sediments of Upper Great Lakes: Insights into Their Origin.

Polyhalogenated carbazoles (PHCZs) have been increasingly detected in the environment. Their similarities in chemical structure with legacy pollutants and their potential toxicity have caused increasing concern. In this work, 112 Ponar grab and 28 core sediment samples were collected from Lakes Michigan, Superior, and Huron, and a total of 26 PHCZs were analyzed along with unsubstituted carbazole using gas chromatography coupled with single- or triple-quadrupole mass spectrometry. Our results show that the total accumulation of PHCZs in the sediments of the upper Great Lakes is >3000 tonnes, orders of magnitude greater than those of polychlorinated biphenyls (PCBs) and decabromodiphenyl ether (BDE209). The 27 individual analytes differ in spatial distribution and temporal trend. Our results showed that PHCZs with substitution patterns of -Br2-5, -Cl1-2Br2-4, or having iodine, were more abundant in sediment of Lake Michigan deposited before 1900 than those deposited more recently, implying a natural origin. Some "emerging" PHCZs have been increasingly deposited into the sediment in recent decades, and deserve further environmental monitoring and research. Other PHCZs with low halogen substitution may form from in situ dehalogenation of PHCZs having more halogens. Anthropogenic sources of PHCZs may exist, particularly for the emerging and low molecular mass congeners.

Organophosphate Esters in Sediment of the Great Lakes.

This is the first study on organophosphate ester (OPEs) flame retardants and plasticizers in the sediment of the Great Lakes. Concentrations of 14 OPEs were measured in three sediment cores and 88 Ponar surface grabs collected from Lakes Ontario, Michigan, and Superior of North America. The sum of these OPEs (Σ14OPEs) in Ponar grabs averaged 2.2, 4.7, and 16.6 ng g-1 dw in Lakes Superior, Michigan, and Ontario, respectively. Multiple linear regression analyses demonstrated statistically significant associations between logarithm concentrations of Σ14OPEs as well as selected congeners in surface grab samples and sediment organic carbon content as well as a newly developed urban distance factor. Temporal trends observed in dated sediment cores from Lake Michigan demonstrated that the recent increase in depositional flux to sediment is dominated by chlorinated OPEs, particularly tris(2-chloroisopropyl) phosphate (TCPP), which has a doubling time of about 20 years. Downward diffusion within sediment may have caused vertical fractionation of OPEs over time. Two relatively hydrophilic OPEs including TCPP had much higher concentrations in sediment than estimated based on equilibria between water and sediment organic carbon. Approximately a quarter (17 tonnes) of the estimated total OPE burden (63 tonnes) in Lake Michigan resides in sediment, which may act as a secondary source releasing OPEs to the water column for years to come.

Debromination of PBDEs in Arkansas Water Bodies Analyzed by Positive Matrix Factorization.

A previously generated data set for polybrominated diphenyl ethers (PBDEs) in dated sediment cores of West Lake of El Dorado (AED), Calion Lake (ACL), and the lagoon of Magnolia Wastewater Treatment Facility (AMW) from Southern Arkansas is examined by a weighted chemical mass balance (CMB) model and positive matrix factorization (PMF) in order to quantify PBDE sources and debromination. DNA extraction and pyrosequencing were done on several core sections in order to investigate microbial debromination. CMB and PMF analyses indicate that deca technical mixtures are the dominant PBDE input (>99% in mole fraction in AED and ACL, and 94.7% in AMW). Minor contributions of penta and octa technical mixtures were found in all three water bodies (<1% in AED and ACL; and 1.1% and 4.1% in AMW, respectively). Results suggest that debromination takes place in all three lakes, but is more intense in AMW. In-situ microbial debromination was supported by the microorganism analysis. The PMF results are validated by PBDE manufacturing records, and the operating history of AMW. Despite the high PBDE concentrations in these sediments near former manufacturing facilities, the extent of debromination is limited, possibly due to sorption to natural organic matter of the sediment.

Untargeted Screening and Distribution of Organo-Bromine Compounds in Sediments of Lake Michigan.

Previously unreported natural and synthetic organo-bromine compounds (NSOBCs) have been found to contribute more than 99% of total organic bromine (TOB) in environmental matrices. We recently developed a novel untargeted method (data-independent precursor isolation and characteristic fragment, DIPIC-Frag) and identified ∼2000 NSOBCs in two sediments from Lake Michigan. In this study, this method was used to investigate the distributions of these NSOBCs in 23 surficial samples and 24 segments of a sediment core from Lake Michigan. NSOBCs were detected in all 23 surficial samples and exhibited 10- to 100-fold variations in peak abundance among locations. The pattern of distributions of NSOBCs was correlated with depth of the water column (r(2) = 0.61, p < 0.001). Hierarchical cluster analysis showed that sediments in close proximity exhibited similar profiles of NSOBCs. Distributions of NSOBCs in 24 segments of a sediment core dated from 1766 to 2008 were investigated, and samples from similar depths exhibited similar profiles of NSOBCs. NSOBCs were grouped into four clusters (soft-cluster analysis) with different temporal trends of abundances. 515 and 768 of the NSOBCs were grouped into cluster 1 and cluster 3 with increasing temporal trends, especially since 1950, indicating that abundances of these compounds might have been affected by human activities.

Occurrence of Atrazine and Related Compounds in Sediments of Upper Great Lakes.

Surface grab and core sediment samples were collected from Lakes Michigan, Superior, and Huron from 2010 to 2012, and concentrations of herbicides atrazine, simazine, and alachlor, as well as desethylatrazine (DEA), were determined. Concentrations of atrazine in surface grabs ranged from 0.01 to 1.7 ng/g dry weight and are significantly higher in the southern basin of Lake Michigan (latitude <44°) than other parts of the three lakes. The highest concentration of alachlor was found in sediments of Saginaw Bay in Lake Huron. The inventory and net fluxes of these herbicides were found to decline exponentially from the south to the north. The concentration ratio of DEA to atrazine (DEA/ATZ) increased with latitude, suggesting degradation of atrazine to DEA during atmospheric transport. DEA/ATZ also increased with sediment depth in the sediment cores. Diffusion of deposited herbicides from the upper sediment into deeper sediments has occurred, on the basis of the observed patterns of concentrations in dated sediment cores. Concentrations of atrazine in pore water were estimated and were higher than those reported for the bulk waters, suggesting the occurrence of solid-phase deposition of atrazine through the water column and that contaminated sediments act as a source releasing atrazine to the overlying water.

Untargeted Screening and Distribution of Organo-Iodine Compounds in Sediments from Lake Michigan and the Arctic Ocean.

The majority of halogenated organic compounds present in the environment remain unidentified. To address this data gap, we recently developed an untargeted method (data-independent precursor isolation and characteristic fragment; DIPIC-Frag) for identification of unknown organo-bromine compounds. In this study, the method was adapted to enable untargeted screening of natural and synthetic organo-iodine compounds (NSOICs) in sediments. A total of 4,238 NSOIC peaks were detected in sediments from Lake Michigan. Precursor ions and formulas were determined for 2,991 (71%) of the NSOIC peaks. These compounds exhibited variations in abundances (<10(3) to ∼10(7)), m/z values (206.9304-996.9474), retention times (1.0-29.7 min), and number of iodine atoms (1-4). Hierarchical cluster analysis showed that sediments in closer proximity exhibited similar profiles of NSOICs. NSOICs were screened in 10 samples of sediment from the Arctic Ocean to compare the profiles of NSOICs between freshwater and marine sediments. A total of 3,168 NSOIC peaks were detected, and profiles of NSOICs in marine sediments were clearly distinct from Lake Michigan. The coexistence of brominated and iodinated analogues indicated that some NSOICs are of natural origin. Different ratios of abundances of iodinated compounds to brominated analogues were observed and proposed as a marker to distinguish sources of NSOICs.

Untargeted Identification of Organo-Bromine Compounds in Lake Sediments by Ultrahigh-Resolution Mass Spectrometry with the Data-Independent Precursor Isolation and Characteristic Fragment Method.

While previous studies have found that unknown natural and synthetic organo-bromine compounds (NSOBCs) contributed more than 99% of the total organic bromine (Br) in the environment, there was no efficient method for untargeted screening to identify NSOBCs in environmental matrixes. A novel untargeted method for identifying NSOBCs, based on ultrahigh-resolution mass spectrometry (UHRMS) with the Q Exactive instrument was developed. This method included a data-independent precursor isolation and characteristic fragment (DIPIC-Frag) procedure to identify NSOBCs. A total of 180 successive 5-m/z-wide windows were used to isolate precursor ions. This resulted in a sufficient dynamic range and specificity to identify peaks of Br fragment ions for analysis. A total of 2520 peaks of NSOBC compounds containing Br were observed in sediments from Lake Michigan, United States. A new chemometric strategy which combined chromatographic profiles, isotopic peaks, precursor isolation window information, and intensities was used to identify precursor ions and chemical formulas for detecting NSOBCs. Precursor ions for 2163 of the 2520 NSOBCs peaks (86%) were identified, and chemical formulas for 2071 NSOBCs peaks (82%) were determined. After exclusion of isotopic peaks, 1593 unique NSOBCs were identified and chemical formulas derived for each. Most of the compounds identified had not been reported previously and had intensities which were 100- to 1000-fold greater than the congeners of polybrominated diphenyl ethers (PBDEs). In extracts of sediments, these compounds exhibited variations in intensities (<10(3) to ∼10(8)), m/z values (170.9438-997.5217), retention times on a C18 column (1.0-29.3 min), and the number of Br atoms (1-8). Generally, compounds with greater m/z values had longer retention times and greater numbers of Br atoms. Three compounds were used in a proof-of-concept experiment to demonstrate that structures of some of the screened NSOBCs could be further predicted by combining searching of database libraries and high-resolution MS(2) spectra.

Polyhalogenated carbazoles in sediments of Lake Michigan: a new discovery.

Previously unknown halogenated compounds were detected during the analysis of halogenated flame retardants in two sediment cores collected from Lake Michigan. Gas chromatography coupled with high- or low-resolution mass spectrometry (MS) was used to determine the chemical structures for a total of 15 novel polyhalogenated carbazoles (PHCs) with the general molecular formula C12H9-x-y-zNClxBryIz. On the basis of the mass spectra generated by electron impact (EI) and electron capture negative ionization (ECNI) MS, eight PHCs were tentatively identified as polybrominated carbazoles, while the others were mixed halogenated carbazoles containing, in addition to bromine, either chlorine or iodine or both. Patterns of halogen substitution of PHCs included Br2 to Br5, ClBr2, ClBr3, ClBr4, ClBr3I, Br4I, and Br3I2. 3,6-Dibromocarbazole and 1,3,6,8-tetrabromocarbazole were also found among the PHCs. Profiles of the concentration versus depth of sediment at the two sites showed various patterns among polybrominated carbazoles. The abundance of mixed halogenated carbazoles peaked at depths of 12-16 cm, remained at relatively constant levels in deeper sediment, but declined markedly in more recently deposited sediments. This is the first study discovering the seven mixed halogenated carbazoles in the environment. Detailed methods for their detection and identification are provided.

Dental composite biodeterioration in the presence of oral Streptococci and extracellular metabolic products.

OBJECTIVE: Secondary caries is a primary cause of early restoration failure. While primary dental caries has been extensively researched, our knowledge about the impact of secondary caries on dental restorations is relatively limited. In this study, we examined how different clinically relevant microbially-influenced environments impact the degradation of nano-filled (FIL) and micro-hybrid (AEL) dental composites. METHODS: Material strength of two commercial dental composites was measured following incubation in aqueous media containing: i) cariogenic (Streptococcus mutans) and non-cariogenic bacteria (Streptococcus sanguinis) grown on sucrose or glucose, ii) abiotic mixtures of artificial saliva and sucrose and glucose fermentation products (volatile fatty acids and ethanol) in proportions known to be produced by these microorganisms, and iii) abiotic mixtures of artificial saliva and esterase, a common oral extracellular enzyme. RESULTS: Nano-filled FIL composite strength decreased in all three types of incubations, while micro-hybrid AEL composite strength only decreased significantly in biotic incubations. The strength of both composites was statistically significantly decreased in all biotic incubations containing both cariogenic and non-cariogenic bacteria beyond that induced by either abiotic mixtures of fermentation products or esterase alone. Finally, there were no statistically significant differences in composite strength decrease among the tested biotic conditions. CONCLUSIONS: The results show that conditions created during the growth of both cariogenic and non-cariogenic oral Streptococci substantially reduce commercial composite strength, and this effect warrants further study to identify the mechanism(s). CLINICAL SIGNIFICANCE: Dental biofilms of oral Streptococci bacteria significantly affect the mechanical strength of dental restorations.

The impact of long-term aging in artificial saliva media on resin-based dental composite strength.

Although salivary liquid can degrade constituents in resin-based dental composites in short-term incubations, there is a knowledge gap on how longer-term aging impacts their bulk strength. We address this through extended aging studies with resin-based dental composites in different environments. Two commercial composites (FIL and AEL) were aged aseptically at 37°C in air (A, control), artificial saliva (AS), and esterase enzyme amended AS (EAS). Diametral and pushout strength were measured after periods of 120-180 days. At 120 days, the diametral strength of composites aged in air was 69.9 ± 11.0 and 57.7 ± 3.31 MPa in FIL and AEL, respectively. These were significantly greater compared to composites aged in AS (32.1 ± 7.01 and 46.2 ± 9.38 MPa in FIL and AEL, respectively) or EAS (36.7 ± 8.49 and 43.5 ± 5.51 MPa in FIL and AEL, respectively). In contrast, pushout strength for both composites were smaller in A compared to those aged in AS and EAS, results attributed to AS absorption and polymer expansion. No significant change in either diametral or pushout strength occurred after 120 days. There was no significant difference between aging in AS and EAS, suggesting that esterase did not significantly decrease the bulk material strength to a greater extent than AS under the test conditions. Aqueous diffusivities for the composites ranged from 8.4 to 11 × 10-13  m2 /s, with associated porosities ranging from 0.06% to 0.10%. These results indicate that saturation of a typical dental composite occurs over a time frame of 4-5 months, longer than typical aging studies. Together, the results demonstrate the importance of aging time on composite strength.

Aqueous Geochemical Controls on the Sestonic Microbial Community in Lakes Michigan and Superior.

Despite being the largest freshwater lake system in the world, relatively little is known about the sestonic microbial community structure in the Laurentian Great Lakes. The goal of this research was to better understand this ecosystem using high-throughput sequencing of microbial communities as a function of water depth at six locations in the westernmost Great Lakes of Superior and Michigan. The water column was characterized by gradients in temperature, dissolved oxygen (DO), pH, and other physicochemical parameters with depth. Mean nitrate concentrations were 32 µmol/L, with only slight variation within and between the lakes, and with depth. Mean available phosphorus was 0.07 µmol/L, resulting in relatively large N:P ratios (97:1) indicative of P limitation. Abundances of the phyla Actinobacteria, Bacteroidetes, Cyanobacteria, Thaumarchaeota, and Verrucomicrobia differed significantly among the Lakes. Candidatus Nitrosopumilus was present in greater abundance in Lake Superior compared to Lake Michigan, suggesting the importance of ammonia-oxidating archaea in water column N cycling in Lake Superior. The Shannon diversity index was negatively correlated with pH, temperature, and salinity, and positively correlated with DO, latitude, and N2 saturation. Results of this study suggest that DO, pH, temperature, and salinity were major drivers shaping the community composition in the Great Lakes.

Stoichiometric models of sucrose and glucose fermentation by oral streptococci: Implications for free acid formation and enamel demineralization.

OBJECTIVES: The objective of this study is to develop stoichiometric models of sugar fermentation and cell biosynthesis for model cariogenic Streptococcus mutans and non-cariogenic Streptococcus sanguinis to better understand and predict metabolic product formation. METHODS: Streptococcus mutans (strain UA159) and Streptococcus sanguinis (strain DSS-10) were grown separately in bioreactors fed brain heart infusion broth supplemented with either sucrose or glucose at 37 °C. Cell mass concentration and fermentation products were measured at different hydraulic residence times (HRT) to determine cell growth yield. RESULTS: Sucrose growth yields were 0.080 ± 0.0078 g cell/g and 0.18 ± 0.031 g cell/g for S. sanguinis and S. mutans, respectively. For glucose, this reversed, with S. sanguinis having a yield of 0.10 ± 0.0080 g cell/g and S. mutans 0.053 ± 0.0064 g cell/g. Stoichiometric equations to predict free acid concentrations were developed for each test case. Results demonstrate that S. sanguinis produces more free acid at a given pH than S. mutans due to lesser cell yield and production of more acetic acid. Greater amounts of free acid were produced at the shortest HRT of 2.5 hr compared to longer HRTs for both microorganisms and substrates. SIGNIFICANCE: The finding that the non-cariogenic S. sanguinis produces greater amounts of free acids than S. mutans strongly suggests that bacterial physiology and environmental factors affecting substrate/metabolite mass transfer play a much greater role in tooth or enamel/dentin demineralization than acidogenesis. These findings enhance the understanding of fermentation production by oral streptococci and provide useful data for comparing studies under different environmental conditions.

Relationships between composite roughness and Streptococcus mutans biofilm depth under shear in vitro.

OBJECTIVE: To investigate the effect of substrate, surface roughness, and hydraulic residence time (HRT) on Streptococcus mutans biofilms growing on dental composites under conditions relevant to the oral cavity. METHODS: Dental composites were prepared with varying amounts of polishing and incubated in a CDC bioreactor with an approximate shear of 0.4 Pa. S. mutans biofilms developed in the bioreactors fed sucrose or glucose and at 10-h or 40-h HRT for one week. Biofilms were characterized by confocal laser microscopy (CLM). Composite surface roughness was characterized by optical profilometry, and pre- and post-incubation composite surface fine structure and elemental composition were determined using scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS). RESULTS: Polishing had a significant impact on surface roughness, varying by a factor of 15 between the polished samples and the unpolished control. S. mutans biofilms grew statistically significantly thicker on the unpolished composites. Biofilm thickness was greater at shorter 10-h HRT compared to 40-h HRT. In most cases, biofilm thickness was not statistically significantly greater in sucrose-fed bioreactors than in glucose-fed bioreactors. SEM-EDS analysis did not identify any significant change in elemental composition after aging. CONCLUSIONS: Accurate characterization of oral cavity biofilms must consider shear forces and the use of techniques that minimize alteration of the biofilm structure. Under shear, surface smoothness is the most important factor determining S. mutans biofilm thickness followed by HRT, while sucrose presence did not result in significantly greater biofilm thickness. CLINICAL SIGNIFICANCE: The obvious patterns of S. mutans growth along sub-micron scale grooving created by the polishing process suggested that initial biofilm attachment occurred in the shear-protected grooves. These results suggest that fine polishing may help prevent the initial formation of S. mutans biofilms compared to unpolished/coarse polished composites.

Field measurements and modeling of ebullition-facilitated flux of heavy metals and polycyclic aromatic hydrocarbons from sediments to the water column.

Gas ebullition-facilitated transport of metals and polycyclic aromatic hydrocarbons (PAHs) from sediment was investigated in 14 urban waterway locations. Gas ebullition varied widely over four seasons (range 2-450 mmol m(-2) d(-1), mean 140 ± 90 mmol m(-2) d(-1)) and was highly temperature dependent. Ebullition-facilitated metal fluxes were large: 50 ± 13 mg m(-2) d(-1) (Fe), 2.6 ± 0.71 mg m(-2) d(-1) (Zn), 1.5 ± 0.28 mg m(-2) d(-1) (Pb), and 0.19 ± 0.06 mg m(-2) d(-1) (Cr). Ebullition-facilitated PAH fluxes were also large: 0.61 ± 0.27 mg m(-2) d(-1) for anthracene, 0.65 ± 0.28 mg m(-2) d(-1) for benzo[a]pyrene, 0.72 ± 0.28 mg m(-2) d(-1) for chrysene, 3.51 ± 1.23 mg m(-2) d(-1) for fluoranthene, 0.23 ± 0.08 mg m(-2) d(-1) for naphthalene, 3.84 ± 1.47 mg m(-2) d(-1) for phenanthrene, and 2.46 ± 0.86 mg m(-2) d(-1) for pyrene. The magnitude of these fluxes indicates that gas ebullition is an important pathway for release of both PAHs and heavy metals from buried sediments. Multivariate regression analysis of the in situ gas ebullition flux and ebullition-facilitated contaminant flux suggests that metal transport likely is due to sediment particle resuspension, whereas PAH transport is due to both contaminant partitioning to gas bubbles and to sediment resuspension. These results indicate that assumptions regarding the natural recovery potential of ebullition-active sediments should be made with caution.

Polybromodiphenyl ethers and decabromodiphenyl ethane in aquatic sediments from southern and eastern Arkansas, United States.

South-central Arkansas (AR) is home to major manufacturing facilities for brominated flame retardant chemicals (BFRs) in the U.S. Unintended release during production may have caused accumulation of the BFRs in the local environment. In this work, sediment cores were collected from six water bodies in AR, including three located close to the BFR manufacturing facilities in El Dorado and Magnolia, to investigate past and recent deposition histories. A total of 49 polybromodiphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) were detected, with concentrations as high as 57000 and 2400 ng/g dry weight for decabromodiphenyl ether (BDE209) and DBDPE, respectively. Log-log regression of BDE209 and DBDPE surface concentrations versus distance to known BFR manufacturing facilities fit the Gaussian Plume Dispersion model, and showed that, if the distance is shortened by half, concentrations of BDE209 and DBDPE would increase by 5-fold. The spatial distribution and temporal trend of the contamination indicate that the manufacturing of PBDEs and DBDPE is the primary source for these compounds in the environment of southern Arkansas. Interestingly, the occurrence of debromination of PBDEs in the sediments of a previously used wastewater sludge retention pond in Magnolia is indicated by the presence of congeners that had not been detected in any commercial PBDE mixtures and by increased fractions of lower brominated congeners relative to higher brominated congeners. Two unknown brominated compounds were detected in the sediments, and identified as nonabromodiphenyl ethanes.

Dynamic models of multi-trophic interactions in microbial food webs.

Non-steady-state mechanistic models were developed to examine the dynamics of organic pollutant utilization, microbial competition, inhibition and predation in a multi trophic system populated by bacteria of different growth rates and protozoa in a continuously mixed flow reactor and a batch reactor. The levels of substrate and cells were modeled during the biodegradation of naphthalene (a moderately bioavailable semi-volatile organic pollutant) by two bacteria in the presence of a predator assuming other nutrients were present in excess. The model predicts that multiple bacteria and predator species can co-exist in the system only if they differ in inhibition capacity, selective predation rate, and/or ability to employ predation defense mechanisms. These models further predict that predation can enhance the process of bioremediation, similar to what has been observed in some experimental studies. Together, these results provide a mechanistic model framework to support the idea that increased species diversity may increase the ability of microbial ecosystems to biodegrade pollutants.

Aeration prevents methyl mercury production in dental wastewater.

Although research has demonstrated that Hg is methylated in the reducing conditions of the dental clinic wastewater collection system, studies are inconclusive as to whether further methylation occurs in the aeration basin of activated sludge wastewater treatment plant (WWTP) which typically treats this waste. Given the high levels of methyl Hg reported in dental wastewater (DWW), it is important to determine whether additional methylation occurs once it enters the WWTP. To achieve this objective, we incubated DWW under conditions designed to mimic the oxidized conditions of the activated sludge aeration basin in a WWTP. Duplicate bioreactors were charged with raw DWW collected from a 12-chair dental clinic and incubated both with and without aeration. Aeration was continued for 15 days, consistent with the typical mean cell residence time (MCRT) necessary for both heterotrophic carbon oxidation (typically 5-6 days) and nitrification (typically 12-15 days), thus ensuring that incubation time exceeded those for most conceivable MCRTs used in the activated sludge process. Results demonstrate a rapid increase in pH concomitant with an increase in dissolved oxygen (DO) to near saturation in the aerated reactor. The non-aerated reactor remained low or at zero DO due to low surface reaeration coupled with the high levels of organic matter. The rate of mercury methylation increased in the unaearated reactors rapidly upon incubation, reaching highest levels when DO was at the lowest levels during the experiment. In great contrast, methyl mercury levels were much lower and net mercury methylation does not appear to occur at any significant rate under aeration. These results imply that although some mercury methylation may occur in the sewer collection system (or anaerobic digesters), net methylation is unlikely to occur in the aeration basin in activated sludge WWTPs, and thus methyl Hg influent levels from DWW represent an upper bound on effluent levels.

Polyhalogenated carbazoles in freshwater and estuarine sediment from China and the United States: A multi-regional study.

The present study represents a multi-regional investigation of polyhalogenated carbazoles (PHCZs) contamination in estuarine and freshwater systems from the United States and China. Although recent studies have suggested that PHCZs are persistent and bioaccumulative, available data are not sufficient to understand their large-scale spatial and temporal distributions in the environment. The present study investigated spatial distributions of PHCZs in surface sediment from multiple freshwater and estuarine systems located in China and the United States (U.S.) during the period of 2012-2017, as well as temporal distributions from vertical trends in selected sediment cores. The results demonstrated large variations of PHCZ contamination across regions, with median concentrations of ΣPHCZs in surface sediment ranging from 3.1 to 134 ng/g. Profiles of PHCZ congener composition also exhibited regional variations and estuarine-freshwater differences. These differences likely reflect the relative contributions of different natural and industrial sources among the locations. Vertical profiles of concentrations and compositions in one Chinese estuarine sediment core and two freshwater sediment cores from the U.S. all demonstrated clear anthropogenic influences to varying degrees. Toxic equivalents (TEQ) of PHCZs were estimated based on their dioxin-like activities, which ranged from <0.001 to 4.94 pg TEQ/g in all sites. The results suggest that PHCZs could add additional ecological risks to the benthos and other aquatic organisms. Our findings constitute an essential contribution to the knowledge body of PHCZ contamination in global aquatic systems and congener-specific contamination characterizations.

Halogenated flame retardants in sediments from the Upper Laurentian Great Lakes: Implications to long-range transport and evidence of long-term transformation.

Most hydrophobic halogenated flame retardants (HFRs) are highly accumulative and persistent in aquatic sediments. The objective of this study was to reveal spatial distributions, temporal trends, and transformation of selected legacy and emerging HFRs in sediments of Lakes Superior, Michigan, and Huron. We collected Ponar grab samples at 112 locations and sediment cores at 28 sites in the three lakes, and measured concentrations of 19 brominated FRs and 12 chlorinated FRs. Based on grab samples, concentrations were higher at southeastern and sites near Sleeping Bear Dunes of Lake Michigan, and Saginaw Bay and the North Channel of Lake Huron. The annual loadings of polybrominated diphenyl either (PBDEs) and Dechlorane Plus (DPs) to sediment have leveled off or been declining since 2000, while loadings of DBDPE and Dec604 have increased since the 1960s in most cores. The concentration ratio of BB101 to BB153 increased with sediment depth, suggesting the occurrence of in situ debromination of BB153. The ratio of dechlorinated anti-Cl11DP over anti-DP increases with the increasing latitude of sampling locations, suggesting the occurrence of dechlorination of anti-DP to anti-Cl11DP during transport. This ratio also increases with increasing sediment age in most cores, implying in situ dechlorination over time.