Potential use of floating treatment wetlands established with Canna flaccida for removing organic contaminants from surface water.

Surface water bodies worldwide may be contaminated with various organic contaminants. In many cases, the actual toxicity thresholds to nontarget organisms are unknown, thus presenting unknown risks. This study evaluated the potential use of floating treatment wetlands (FTWs) planted with Canna flaccida (common name: Canna) for removing two pharmaceuticals (acetaminophen and carbamazepine) and one herbicide (atrazine) from contaminated water. Triplicate FTWs with varying plant densities were established in 378 L mesocosms. After dosing the mesocosms with the contaminants, water samples were collected over a 12-week period for analysis. The planted FTWs showed differing abilities for removing acetaminophen, atrazine, and carbamazepine. Plant densities on the FTWs did not affect dissipation of acetaminophen or atrazine, but did carbamazepine. All acetaminophen residues were removed from the water within 2 weeks, while all atrazine residues were removed within 12 weeks. Approximately, 79-92% of these residues removed were associated with the FTWs. In contrast, all of the carbamazepine was not removed after 12 weeks, at which time only 29-36.7% of the total removed was associated with the FTWs. Overall results suggest that FTWs established with C. flaccida are promising for removing trace concentrations of acetaminophen, atrazine, and carbamazepine from surface water.

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.

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.

Silver nanoparticle exposure attenuates the viability of rat cerebellum granule cells through apoptosis coupled to oxidative stress.

The impact of silver nanoparticles (AgNPs) on the central nervous system is a topic with mounting interest and concern and the facts remain elusive. In the current study, the neurotoxicity of commercial AgNPs to rat cerebellum granule cells (CGCs) and the corresponding molecular mechanism are closely investigated. It is demonstrated that AgNPs induce significant cellular toxicity to CGCs in a dose-dependent manner without damaging the cell membrane. Flow cytometry analysis with the Annexin V/propidium iodide (PI) staining indicates that the apoptotic proportion of CGCs upon treatment with AgNPs is greatly increased compared to the negative control. Moreover, the activity of caspase-3 is largely elevated in AgNP-treated cells compared to the negative control. AgNPs are demonstrated to induce oxidative stress, reflected by the massive generation of reactive oxygen species (ROS), the depletion of antioxidant glutathione (GSH), and the increase of intracellular calcium. Histological examination suggests that AgNPs provoke destruction of the cerebellum granular layer in rats with concomitant activation of caspase-3, in parallel to the neurotoxicity of AgNPs observed in vitro. Taken together, it is demonstrated for the first time that AgNPs substantially impair the survival of primary neuronal cells through apoptosis coupled to oxidative stress, depending on the caspase activation-mediated signaling.

Identification of tetrabromobisphenol A allyl ether and tetrabromobisphenol A 2,3-dibromopropyl ether in the ambient environment near a manufacturing site and in mollusks at a coastal region.

Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants (BFRs) and has been frequently detected in the environment and biota. Recent studies have found that derivatives of TBBPA, such as TBBPA bis(allyl) ether (TBBPA BAE) and TBBPA bis(2,3-dibromopropyl) ether (TBBPA BDBPE) are present in various environmental compartments. In this work, using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) and liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (LC-Q-TOF-MS), TBBPA allyl ether (TBBPA AE) and TBBPA 2,3-dibromopropyl ether (TBBPA DBPE) were identified in environmental samples and further confirmed by synthesized standards. Soil, sediment, rice hull, and earthworm samples collected near a BFR manufacturing plant were found to contain these two compounds. In sediments, the concentrations of TBBPA AE and TBBPA DBPE ranged from 1.0 to 346.6 ng/g of dry weight (dw) and from 0.7 to 292.7 ng/g of dw, respectively. TBBPA AE and TBBPA DBPE in earthworm and rice hull samples were similar to soil samples, which ranged from below the method limit of detection (LOD, <0.002 ng/g of dw) to 0.064 ng/g of dw and from below the LOD (<0.008 ng/g of dw) to 0.58 ng/g of dw, respectively. Furthermore, mollusks collected from the Chinese Bohai Sea were used as a bioindicator to investigate the occurrence and distribution of these compounds in the coastal environment. The detection frequencies of TBBPA AE and TBBPA DBPE were 41 and 32%, respectively, and the concentrations ranged from below LOD (<0.003 ng/g of dw) to 0.54 ng/g of dw, with an average of 0.09 ng/g of dw, for TBBPA AE, and from below LOD (<0.008 ng/g of dw) to 1.41 ng/g of dw, with an average of 0.15 ng/g of dw, for TBBPA DBPE.

Estrogen-like response of perfluorooctyl iodide in male medaka (Oryzias latipes) based on hepatic vitellogenin induction.

Using the in vivo male medaka model, we investigated the estrogen-like response of perfluorooctyl iodide (PFOI) which is a potential source of perfluorinated carboxylic acids. Using real-time quantitative polymerase chain reaction, the expression levels of related estrogenic genes including estrogenic receptor α (ERα), ERß, vitellogenin I (VTG I), and VTG II in the livers of male medaka exposed to PFOI were analyzed. The results showed that PFOI upregulated the expression levels of the tested genes in a dose-dependent manner. VTG protein levels increased in both dose- and time-dependent manners due to PFOI exposure. The results suggested that PFOI is a potential estrogenic compound.

Quantifying the effects of anaerobic soil disinfestation and other biological soil management strategies on nitrous oxide emissions from raised bed plasticulture tomato production.

Soilborne pests are a major obstacle that must be overcome for the production of horticultural crops. Methyl bromide (MBr) was an effective preplanting soil broad-spectrum biocide, but its use has been banned due to its role in depleting the ozone layer. As a result, sustainable alternative methods for controlling soilborne pathogens and pests are needed. Nitrous oxide (N2 O) emissions are of concern in crop production due to the role of N2 O as a greenhouse gas. Agricultural lands are known sources for emission of N2 O into the atmosphere. Emissions are related to many environmental factors as well as fertilization and fumigation practices. This study evaluated the influence of different alternatives to MBr on N2 O emissions throughout a tomato production season in two locations representative of southern and northern Florida. We evaluated eight soil management practices, including (a) untreated controls; (b) chemical soil fumigation; (c) anaerobic soil disinfestation using molasses (M) + composted poultry litter and (d and e) M + composted yard waste (CYW, at two rates); (f) Soil Symphony Amendment (SSA), a commercially available mix of microbes and nutrients; (g) CYW alone; and (h) CYW + SSA. Nitrous oxide emissions were measured throughout the cropping season. Emissions were highest on the day of planting (Day 21), ranging from 213 to 1,878 µg m-2 h-1 , likely due to the release of N2 O that had accumulated under the totally impermeable film when it was punctured for planting. However, statistical significance varied between sites. Estimated cumulative emissions of N2 O throughout the production season ranged from 1.3 to 4.8 kg N2 O-N ha-1 .

Identification of tetrabromobisphenol A diallyl ether as an emerging neurotoxicant in environmental samples by bioassay-directed fractionation and HPLC-APCI-MS/MS.

Brominated flame retardants (BFRs) have been widely used as additives in products to reduce their flammability. Recent findings suggested that some BFRs exhibit neurotoxicity and thus might pose a threat to human health. In this work, a neurotoxicity assay-directed analysis was developed, combining sample cleanup, fractionation, chemical identification, and bioassay. Viability of primary cultured cerebellar granule neurons (CGNs) was used to evaluate the neurotoxicity of extracts or separated fractions from environmental samples. Tetrabromobisphenol A diallyl ether (TBBPA DAE) was identified as the causative toxicant in sediment samples collected from a river near a brominated flame retardant (BFR) manufacturing plant in South China. Liquid chromatography atmospheric pressure chemical ionization tandem mass spectrometry (LC-APCI-MS/MS) was optimized to determine TBBPA DAE levels in the potent fractions and to confirm TBBPA DAE as the key neurotoxicant. On the basis of comparison with the structure of other TBBPA derivatives, the 1-propenyl group in TBBPA DAE appears to be the cause for the neurotoxic potency. The levels of TBBPA DAE in samples along the river were found at up to 49 ng/L for river water, 10,183 ng/g dry weight (dw) in surface sediments, and 42 ng/g dw in soils. According to the distribution of TBBPA DAE in the environmental samples, the manufacturing plant was identified as the release source of TBBPA DAE. To our knowledge, this study is the first to demonstrate potential neurotoxicity induced by TBBPA DAE in real environmental samples.

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.

Dissipation of fomesafen in fumigated, anaerobic soil disinfestation-treated, and organic-amended soil in Florida tomato production systems.

BACKGROUND: Fumigated, anaerobic soil disinfestation-treated (ASD), and organic-amended soil management strategies have been investigated as potential methyl bromide (MBr) alternatives for controlling diseases, nematodes, and weeds in soil. Nutsedge and broadleaf weed control using fomesafen has been reported to be comparable to MBr in normal cropping systems. There is no information on the fate of fomesafen used in combination with alternative practices. In this study, the fate of fomesafen in these alternative systems was measured by liquid chromatography-tandem mass spectrometry (LC/MS-MS) following extraction using a modified Quick Easy Cheap Effective Safe (QuEChERS) method. RESULTS: The reported half-life (DT50 ) values for fomesafen in the top 15 cm of soil were from 62.9 to 107.3 days. The DT50 values in organic-amended soil were higher than in ASD-treated soil in the top 15 cm. For all treatments, reductions in concentrations were positively correlated with lower redox potentials and organic matter content. Some leaching of fomesafen into the 16-30 cm zone was observed in all treatments. CONCLUSIONS: The DT50 values in this study were generally higher than those reported in previous studies performed at different locations. Due to increased losses of the herbicide and subsequent reduction in weed control, fomesafen is likely not to be suitable for effective weed control in systems using ASD techniques employing composted poultry litter and molasses. Integration of fomesafen using composted yard waste 1 (CYW1) and Soil Symphony Amendment (SSA) may result in acceptable weed control. Given that the soil was very sandy and the pH was higher than the pKa, fomesafen might leach deeper than 30 cm, particularly with the use of chemical soil fumigants (CSFs). © 2019 Society of Chemical Industry.

[Spectroscopy study of methyl parathion molecularly imprinted polymers].

Three molecularly imprinted polymers were synthesized with different functional monomers respectively, using methyl parathion as the template. These monomers are methacrylic acid, acrylamide and 4-vinylpyridine. According to the UV spectrum study the interaction between methyl parathion and 4-vinylpyridine was stronger than that of the others. Comparably, the infrared spectrum study showed the same results which indicated that 4-vinylpyridine could associate with the template at two different kinds of binding sites, the P-O-C and the -NO2 site, and is most likely to form steady covalent bonds with methyl parathion, while the other two monomers could only associate with the template at the P-O-C site. Furthermore, the infrared spectra of the synthesized polymers confirmed the existence of the functional groups in each kind of polymer, which might interact with the template.

Method development for simultaneous analyses of multiple legacy and emerging organic chemicals in sediments.

The objective of this work was to investigate the feasibility of using a single pretreatment procedure for the analyses of multiple groups of organics, which have a wide range of chemical structures and physicochemical properties, in sediment samples. Nine groups of 162 individual compounds (including 11 surrogates) were investigated, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs), polychlorinated naphthalenes (PCNs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), novel halogenated flame retardants (nXFRs), musk fragrances (MFs) and organophosphate flame retardants (OPFRs). The individual and grouped recoveries of spiked analytes from adsorption chromatographic columns using either only fully activated, neutral silica gel (SG) or the combinations of silica gel and alumina (Si/Al) sorbents were compared. The results showed a generally stronger adsorption and more effective fractionation on the Si/Al column than on the SG column. The dependence of fractionation on halogen substitution, molecular planarity, and polar functional groups was discussed. The effects of adding sulfuric acid with two different methods were investigated, and the recoveries of a number of MFs, OCPs, nXFRs and OPFRs were recovered less than 60%. Sodium hydroxide treatment of silica gel had minor effects on some OPFRs. Copper used to remove elemental sulfur did not affect the recoveries of all target analytes except chloroneb. The finalized method was validated by spiking the target analysts into the sediment samples and comparing the analytical results of this work on two standard reference materials for sediment (SRMs 1941b and 1944) with the certified or reference values.

Effects of polycyclic musks HHCB and AHTN on steroidogenesis in H295R cells.

1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(γ)-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN) are widely used in personal care products. Previous studies showed that HHCB and AHTN can be found in various environmental matrices and have potential endocrine disrupting effects. However, the effects on adrenocortical function of HHCB and AHTN are not fully understood. This study evaluated the influences of HHCB and AHTN on seven steroid hormones (progesterone, aldosterone, cortisol, 17α-OH-progesterone, androstenedione, 17ß-estradiol, and testosterone) and 10 genes involved in steroidogenic pathways (HMGR, StAR, CYP11A1, 3ßHSD2, CYP17, CYP21, CYP11B1, CYP11B2, 17ßHSD, and CYP19) using the H295R cell line in the absence and presence of 8-Br-cAMP. MC2R transcription on the cell membrane was also examined to further investigate the effects of HHCB and AHTN on adrenal steroidogenesis. The results demonstrated that HHCB and AHTN could inhibit progesterone and cortisol production mainly by the suppression of 3ßHSD2 and CYP21. Meanwhile, high concentrations of AHTN can affect the sensitivity of H295R cells to ACTH by disrupting MC2R transcription. Overall, the results indicate that high concentrations of HHCB and AHTN can affect steroidogenesis in vitro using the H295R cell line.