The Ins and Outs of Per- and Polyfluoroalkyl Substances in the Great Lakes: The Role of Atmospheric Deposition.

As part of the Integrated Atmospheric Deposition Network, precipitation (n = 207) and air (n = 60) from five sites and water samples (n = 87) from all five Great Lakes were collected in 2021-2023 and analyzed for 41 per- and polyfluoroalkyl substances (PFAS). These measurements were combined with other available data to estimate the mass budget for four representative compounds, PFBA, PFBS, PFOS, and PFOA for the basin. The median Σ41PFAS concentrations in precipitation across the five sites ranged between 2.4 and 4.5 ng/L. The median Σ41PFAS concentration in lake water was highest in Lake Ontario (11 ng/L) and lowest in Lake Superior (1.3 ng/L). The median Σ41PFAS concentration in air samples was highest in Cleveland at 410 pg/m3 and lowest at Sleeping Bear Dunes at 146 pg/m3. The net mass transfer flows were generally negative for Lakes Superior, Michigan, and Huron and positive for Lakes Erie and Ontario, indicating that the three most northern lakes are accumulating PFAS and the other two are eliminating PFAS. Atmospheric deposition is an important source of PFAS, particularly for Lake Superior.

Per- and Polyfluoroalkyl Substances in Canadian Fast Food Packaging.

A suite of analytical techniques was used to obtain a comprehensive picture of per- and polyfluoroalkyl substances (PFAS) in selected Canadian food packaging used for fast foods (n = 42). Particle-induced gamma ray emission spectroscopy revealed that 55% of the samples contained <3580, 19% contained 3580-10 800, and 26% > 10 800 µg F/m2. The highest total F (1 010 000-1 300 000 µg F/m2) was measured in molded "compostable" bowls. Targeted analysis of 8 samples with high total F revealed 4-15 individual PFAS in each sample, with 6:2 fluorotelomer methacrylate (FTMAc) and 6:2 fluorotelomer alcohol (FTOH) typically dominating. Up to 34% of the total fluorine was released from samples after hydrolysis, indicating the presence of unknown precursors. Nontargeted analysis detected 22 PFAS from 6 different groups, including degradation products of FTOH. Results indicate the use of side-chain fluorinated polymers and suggest that these products can release short-chain compounds that ultimately can be transformed to compounds of toxicological concern. Analysis after 2 years of storage showed overall decreases in PFAS consistent with the loss of volatile compounds such as 6:2 FTMAc and FTOH. The use of PFAS in food packaging such as "compostable" bowls represents a regrettable substitution of single-use plastic food packaging.

From watersheds to dinner plates: Evaluating PFAS exposure through fish consumption in Southeast Michigan.

Muscle tissue and organ samples of six different fish species were collected from ten locations in Southeast Michigan's Huron and Rouge watersheds. Per- and polyfluoroalkyl substances (PFAS) were analyzed in 36 samples comprising filets, liver, gut, and eggs using targeted analysis and the direct total oxidizable precursor (dTOP) assay on a subset of six samples. The median concentrations of the ∑PFAS in filets from the Huron and Rouge watersheds were 13 and 6.3 ng/g wet weight (w.w.), respectively. Perfluorooctane sulfonate (PFOS) was the most detected and abundant compound in fish organs, with the liver having the largest overall burden of PFAS. The highest percent increase in targeted PFAS after the dTOP assay was observed in the Catfish filet (552%) while the smallest increase was in the Catfish liver (32%) accounting for 1.3 and 8.1 nMole F/g dry weight (d.w.), respectively. The positive matrix factorization (PMF) analysis revealed three distinct PFAS sources, of which the one attributed to PFOS explained 73% of the data. Results from this work have important implications for fish consumption in Michigan waterways. Among the filet samples analyzed, the calculated daily consumption limit of total PFOS was exceeded in approximately 82% and 91% of samples for adults and children over the age of seven years old, respectively.

Comparison between guide plate navigation and virtual fixtures in robot-assisted osteotomy.

To verify the advantages of Virtual Fixtures (VFs) by comparing the result of guide plate navigation (GPN) and VFs in robot-assisted osteotomy. Robot-assisted surgery has been extensively applied in traditional orthopedic surgeries. It fundamentally improves surgeries' cutting accuracy. In addition, many key techniques have been applied in bone cutting to increase the procedure's safety in various ways. In this paper, two robot-assisted osteotomy methods are proposed. Three operators with no osteotomy experience performed plane cutting with the assistance of a robot. GPN and VFs were applied to assist the Sawbones cutting. Each operator has five attempts using each method to perform bone cutting, distance errors and angular errors were recorded. The advantage of Sawbones is that there is no influence from soft tissues and blood. It can give a more precise measurement. The results show that both methods have high accuracy with the robot's assistance. VFs have higher accuracy in comparison with GPN. With GPN, the mean distance and angular error of the three operators were 2.974 ± 0.282 mm and 4.737 ± 0.254°. With VFs, the mean range and angular error of the three operators were 1.857 ± 0.349 mm and 2.24 ± 0.123°, respectively. VFs limited the robot's end in the planned area, increasing the accuracy and safety of robot-assisted osteotomy.

Ubiquity of Amino Accelerators and Antioxidants in Road Dust from Multiple Land Types: Targeted and Nontargeted Analysis.

Amino accelerators and antioxidants (AAL/Os), as well as their degradation derivatives, are industrial additives of emerging concern due to their massive production and use (particularly in rubber tires), pervasiveness in the environment, and documented adverse effects. This study delineated their inter-regional variations in road dust collected from urban/suburb, agricultural, and forest areas, and screened for less-studied AAL/O analogues with high-resolution mass spectrometry. 1,3-Diphenylguanidine (DPG; median concentration: 121 ng/g) and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine quinone (6PPD-Q; 9.75 ng/g) are the most abundant congeners, constituting 69.7% and 41.4% of the total concentrations of AAL/Os (192 ng/g) and those of AAO transformation products (22.3 ng/g), respectively. The spatial distribution across the studied sites suggests evident human impacts, reflected by the pronounced urban signature and vehicle-originated pollution. Our nontargeted analysis of the most-contaminated road dust identified 16 AAL/O-related chemicals, many of which have received little investigation. Particularly, environmental and toxicological information remains extremely scarce for five out of the 10 most concerning compounds prioritized in terms of their dusty residues and toxicity including 1,2-diphenyl-3-cyclohexylguanidine (DPCG), N,N''-bis[2-(propan-2-yl)phenyl]guanidine (BPPG), and N-(4-anilinophenyl)formamide (PPD-CHO). Additionally, dicyclohexylamine (DChA), broadly applied as an antioxidant in automobile products, had an even greater median level than DPG. Therefore, future research on their health risks and (eco)toxic potential is of high importance.

Socio-Economic Factors Impact US Dietary Exposure to Halogenated Flame Retardants.

Although diet is an important route of exposure for brominated flame retardants (BFRs), little is known of their presence in US food. Therefore, we purchased meat, fish, and dairy product samples (n = 72) in Bloomington, IN, from 3 stores representing national retail chains at different price levels. Composite samples (n = 42) were analyzed for polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), novel BFRs (NBFRs), and dechlorane plus (DP). Concentrations of total halogenated flame retardants (HFRs) ranged between 54 and 1,400 pg/g ww, with PBDEs being the predominant compounds. Concentrations of NBFRs, but not PBDEs, in US food items were significantly impacted by price, raising the issue of environmental justice. Nonorganic food generally had a higher abundance of BDE-209 than organic food items. Estimates of dietary exposure revealed that meat and cheese consumption contribute most to the overall HFR intake and that intakes are highest for children and for non-Hispanic Asians. Taking into account several caveats and limitations of this study, these results as a whole suggest that health burdens from dietary exposure to HFRs have become minimal for US citizens, highlighting the positive impact of regulatory efforts.

Degradation of 1,4-dioxane by heterogeneous photocatalysis and a photo-Fenton-like process under fluorescent light.

The overall objective of this study was to develop cost-effective treatment processes for 1,4-dioxane removal that were safe and easy to scale up. Degradation of 1,4-dioxane was conducted and compared for the first time by heterogeneous photocatalysis and a photo-Fenton-like process under cool white fluorescent light in mild conditions, using two types of commercial nanoparticles-titanium dioxide (TiO2) and nanoscale zero-valent iron (nZVI), respectively. Both types of nanoparticles removed >99.9% of 1,4-dioxane in a short period of time. Hydroxyl radicals (·OH), superoxide radicals (·O2-), and hydrogen peroxide (H2O2) were detected in both degradation processes; photogenerated holes (h+) were critical in the degradation of 1,4-dioxane by the photocatalytic process using TiO2. 1,4-Dioxane can be degraded at pH 7 in TiO2/light system and at pH 3 in nZVI/light system, and faster degradation of 1,4-dioxane at even higher concentration was achieved in the former system. Increase in light intensity accelerated 1,4-dioxane degradation, which followed first order kinetics in both systems. In wastewater effluent, the removal of 1,4-dioxane was slower than that in deionised water, which likely reflected the complex compositions of the wastewater effluent. Under combined UVA and visible light illumination, a two-stage degradation process was proposed for 1,4-dioxane for the first time by TiO2 nanoparticles; this study also demonstrated for the first time 1,4-dioxane degradation by the photo-Fenton-like process using nZVI. The cost-effective solutions using commercial nanoparticles under fluorescent light developed in this study can be potentially applied to treat water contaminated by high concentrations of 1,4-dioxane in large-scale.

Degradation of perfluoroalkyl substances using UV/Fe0 system with and without the presence of oxygen.

The wide presence of per- and poly-fluoroalkyl substances (PFAS) in the environment is a global concern, thus their degradation is an imminent task. In this study, oxidative and/or reductive degradation of three representative PFAS - perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS) was achieved using nanoscale zero-valent iron (Fe0 NPs) under ultraviolet (UV) light, both with and without the presence of oxygen. Higher degradation and defluorination rates were obtained for a longer chain PFNA compared to PFOA, and a higher removal of PFAS was achieved without the presence of O2 compared to that with O2. The degradation followed first-order reaction kinetics, and obtained the highest rates of 97.6, >99.9, and 98.5% without the presence of O2 for PFOA, PFNA, and PFOS, respectively. The degradation rates increased with an increase in the nanoparticle concentrations in the range of 1-100 mg/L. In addition to fluoride ions, shorter chain perfluorocarboxylic acids (PFCAs) were detected as the main intermediates during PFAS degradation; PFHpS and 6:2 FTS were also detected during PFOS degradation. Hydroxyl radicals (·OH) and superoxide radicals (·O2-) were not involved in the degradation of PFOA, but likely involved in the degradation of PFOS. Emerging contaminants PFAS degradation using the UV/Fe0 system is a cost-effective technology owing to the low cost and recyclability of Fe0 nanomaterials, low energy consumption in the system, and its capability to degrade PFAS both with and without the presence of oxygen. This technology can be potentially applied to treat PFAS-contaminated waters in the environment.

The midcortical-line is more reliable than the T-line in predicting stem anteversion in patients with developmental hip dysplasia after total hip arthroplasty.

Background: Precise preoperative planning improves postoperative outcomes in total hip arthroplasty (THA), especially in developmental dysplasia of the hip (DDH) cases. Previous studies used the T-line and midcortical-line as preoperative landmarks to predict postoperative stem anteversion (PSA). However, the most reliable landmark in predicting PSA in DDH patients remains unclear. To find the most reliable measurement to predict the PSA in DDH patients, this study compared the midcortical-line and T-line at different femoral neck levels. Methods: Pre- and postoperative Computed Tomography (CT) scans of 28 hips in 21 DDH patients who received THA were obtained for three-dimensional femoral models. The preoperative CT scan was used to measure the anteversion of the midcortical-line on the axial cross-sectional plane images (AM-CT), the anteversion of the midcortical-line from 3D models (AM-3D), and the T-line from 3D models (AT-3D) at simulated osteotomy planes at 5 and 10 mm heights proximal to the base of the lesser trochanter. The correlation between the preoperative femoral anteversion (AM-CT, AM-3D, AT-3D) and the PSA was assessed to evaluate the prediction accuracy. Results: The correlations between the AM-CT and the PSA were 0.86 (mean difference (MD) = 1.9°) and 0.92 (MD = -3.0°) at 5 and 10 mm heights, respectively. The correlation between the AM-3D and the PSA were 0.71 (MD = -11.6°) and 0.61 (MD = -12.9°) at 5 and 10 mm heights. The AT-3D was significantly greater (MD = 15.4°) than the PSA (p-value <0.01) at 5 mm cutting height, and the correlation between the AT-3D and the PSA was 0.57 (MD = 7.8°) at 10 mm cutting height. Conclusions: The AM-CT at the 10 mm height had the strongest correlation with the PSA and was more reliable in predicting the PSA when compared with the AM-3D and the AT-3D in DDH patients.

Per- and Polyfluoroalkyl Substances in North American School Uniforms.

We analyzed 72 children's textile products marketed as stain-resistant from US and Canadian stores, particularly school uniforms, to assess if clothing represents a significant route of exposure to per- and polyfluoroalkyl substances (PFAS). Products were first screened for total fluorine (total F) using particle-induced γ-ray emission (PIGE) spectroscopy (n = 72), followed by targeted analysis of 49 neutral and ionic PFAS (n = 57). PFAS were detected in all products from both markets, with the most abundant compound being 6:2 fluorotelomer alcohol (6:2 FTOH). Total targeted PFAS concentrations for all products collected from both countries ranged from 0.250 to 153 000 ng/g with a median of 117 ng/g (0.0281-38 100 µg/m2, median: 24.0 µg/m2). Total targeted PFAS levels in school uniforms were significantly higher than in other items such as bibs, hats, stroller covers, and swimsuits, but comparable to outdoor wear. Higher total targeted PFAS concentrations were found in school uniforms made of 100% cotton than synthetic blends. Perfluoroalkyl acids (PFAAs) precursors were abundant in school uniforms based on the results of hydrolysis and total oxidizable precursor assay. The estimated median potential children's exposure to PFAS via dermal exposure through school uniforms was 1.03 ng/kg bw/day. Substance flow analysis estimated that ∼3 tonnes/year (ranging from 0.05 to 33 tonnes/year) of PFAS are used in US children's uniforms, mostly of polymeric PFAS but with ∼0.1 tonne/year of mobile, nonpolymeric PFAS.

Antibacterial activity of γFe2 O3 /TiO2 nanoparticles on toxic cyanobacteria from a lake in Southern Illinois.

Frequent outbreaks of harmful algal blooms (HABs) have brought adverse impacts on human health, economic viability, and recreational activities in many communities in the United States. Cyanobacteria (or blue-green algae) blooms are the most common type of HABs in surface water. Current bactericides for controlling the blooms are disadvantageous due to the recycling difficulty. In this study, an innovative magnetic nanomaterial-γFe2 O3 /TiO2 nanoparticle-was used to inactivate toxic cyanobacteria species found in a lake in Southern Illinois that frequently experienced HABs. Cyanotoxin genes of mcy, nda, cyr, and sxt were used for targeting microcystin-, nodularin-, cylindrospermopsin-, and saxitoxin-producing cyanobacteria, respectively, by quantitative polymerase chain reaction (PCR) method. It was found that the concentration of chlorophyll a presents a strong correlation (R2 = 0.6024) with the gene copy obtained from 16S rRNA targeted for all cyanobacteria, but not with that from individual toxigenic cyanobacteria. The inactivation efficiencies of the nanomaterials under visible light were as high as 5-log and 1-log for cyanobacteria species containing mcyE/ndaF and sxtA genes, respectively, an improvement over the treatment under darkness. These nanomaterials can be recycled by their magnetic properties for reuse. Communities susceptible to HAB outbreaks are expected to benefit from the developed method for mitigating the blooms. PRACTITIONER POINTS: Lab-made γFe2 O3 /TiO2 nanoparticles can be used to inactivate microcystin/nodularin- and saxitoxin-producing cyanobacteria species. qPCR method can be used for targeting toxic cyanobacteria; Chl a cannot be used as a standalone indicator for HABs. Better inactivation efficiency under visible light indicated possible application of the technology under sunlight for HAB mitigation from surface water.

1,4-Dioxane-contaminated groundwater remediation in the anode chamber of a microbial fuel cell.

A two-chambered microbial fuel cell (MFC) was used for the first time for the remediation of an emerging contaminant-1,4-dioxane in its anode chamber. Groundwater historically detected 1,4-dioxane contamination was sampled from a Superfund site. Comparative study was carried out between metabolic (i.e., 1,4-dioxane as sole carbon source) and cometabolic (i.e., 1,4-dioxane and methanol as carbon sources) anodic degradations. It was found that cometabolic degradation increased 1,4-dioxane removal by 10%-52% after 7 days and increased maximum power production of the MFC by 18% to 88.9 mW/m3 . Oxalic acid was detected as a main metabolic degradation product. Beside oxalic acid, acetic acid and isopropanol were also detected as main products for cometabolic degradation. The presence of a biofilm for 1,4-dioxane anodic degradation was observed by a scanning electron microscopy. Phyla of Bacteroidetes, Firmicutes, and Proteobacteria, as well as a variety of species, were identified for the first time-especially Rikenella sp. and Solitalea canadensis, whose relative abundances were the highest of 18.8% and 24.0% for metabolic and cometabolic degradation, respectively. This study provided an innovative and sustainable approach for 1,4-dioxane anodic biodegradation, which would be potentially utilized for remediation of groundwater contaminated by 1,4-dioxane. PRACTITIONER POINTS: Groundwater contaminated with 1,4-dioxane was remediated in the anode chamber of a two-chambered microbial fuel cell. Cometabolic pathway increased 1,4-dioxane removal and power production of the MFC compared to metabolic pathway. The presence of a biofilm for 1,4-dioxane anodic degradation was observed, and oxalic acid was a main degradation product. This study would be potentially utilized for 1,4-dioxane-contaminated groundwater remediation with simultaneous energy production. External voltage supply for bioelectrochemical remediation of groundwater would potentially be reduced when treating chlorinated hydrocarbons co-occurred with 1,4-dioxane.

Immobilization of lipase on porous monodisperse chitosan microspheres.

Porous monodisperse chitosan microspheres were synthesized for enzyme immobilization. The microspheres were prepared using microchannels and modified with glutaraldehyde. The microspheres had a mean diameter of 495 µm; the polydispersity indices were less than 0.08, and the specific surface area was between 121 and 173 m(2) /g. Candida sp. 1619 lipase was selected as a model lipase. Immobilization conditions such as enzyme loading, glutaraldehyde concentration, and immobilization time were optimized. The temperature, pH, and storage stability of the free and immobilized enzymes were also investigated. The immobilized enzyme had broad-ranging pH and temperature optima as compared with free enzyme. The storage stability of the immobilized enzyme was higher than that of the free enzyme.

Statistical analysis and modeling of pelletized cultivation of Mucor circinelloides for microbial lipid accumulation.

Microbial oil accumulation via oleaginous fungi has some potential benefits because filamentous fungi can form pellets during cell growth and these pellets are easier to harvest from the culture broth than individual cells. This research studied the effect of various culture conditions on the pelletized cell growth of Mucor circinelloides and its lipid accumulation. The results showed that cell pelletization was positively correlated to biomass accumulation; however, pellet size was negatively correlated to the oil content of the fungal biomass, possibly due to the mass transfer barriers generated by the pellet structure. How to control the size of the pellet is the key to the success of the pelletized microbial oil accumulation process.

A new cultivation method for microbial oil production: cell pelletization and lipid accumulation by Mucor circinelloides.

The recent energy crisis has triggered significant attention on the microbial synthesis of lipids, which comprise the raw material for biodiesel production. Microbial oil accumulation with filamentous fungi has great potential because filamentous fungi can form pellets during cell growth, and these pellets are much easier to harvest from cell broth. This paper focuses on the cell pelletization process of the oleaginous Mucor circinelloides. We have studied the effect of various cultural conditions on pelletized cell growth and lipid accumulation. This study is the first to report that pH adjustment during cell growth plays a key role in pellet formation of M. circinelloides and describes a handy method by which to induce cell pelletization in submerged fungal cultivation. Our study reveals that cell growth and lipid production are not significantly affected by pelletization and that lipid accumulation is triggered at stressed conditions, such as a high carbon-to-nitrogen ratio and high temperature.

Direct growth of human enamel-like calcium phosphate microstructures on human tooth.

Dental Enamel is the hardest mineralized tissue in the human body which is comprised of nanorod-like hydroxyapatite crystals arranged into a highly organized micro-architectural unit called an enamel prism. In this paper the direct growth of human enamel-like structures on human tooth using fluorapatite/phosphoric acid pastes is explored. SEM images show that the newly formed calcium phosphate crystals can be self-assembled into a similar ordered microstructure as those seen in human enamel. The mechanism of how these structures form is discussed. This work demonstrates the potential of applying nanotechnology to regenerate dental enamel clinically without cells.