Stormwater biofilter response to high nitrogen loading under transient flow conditions: Ammonium and nitrate fates, and nitrous oxide emissions.

Nitrogen (N) in urban runoff is often treated with green infrastructure including biofilters. However, N fates across biofilters are insufficiently understood because prior studies emphasize low N loading under laboratory conditions, or use "steady-state" flow regimes over short time scales. Here, we tested field scale biofilter N fates during simulated storms delivering realistic transient flows with high N loading. Biofilter outflow ammonium (NH4+-N) was 60.7 to 92.3% lower than that of the inflow. Yet the characteristic times for nitrification (days to weeks) and denitrification (days) relative to N residence times (7 to 30 h) suggested low N transformation across the biofilters. Still, across 7 successive storms, total outflow nitrate (NO3--N) greatly exceeded (3100 to 3900%) inflow nitrate, a result only explainable by biofilter soil N nitrification occurring between storms. Archaeal, and bacterial amoA gene copies (2.1 × 105 to 1.2 × 106 gc g soil-1), nitrifier presence by16S rRNA gene sequencing, and outflow δ18O-NO3- values (-3.0 to 17.1 ‰) reinforced that nitrification was occurring. A ratio of δ18O-NO3- to δ15N-NO3- of 1.83 for soil eluates indicated additional processes: N assimilation, and N mineralization. Denitrification potential was suggested by enzyme activities and soil denitrifying gene copies (nirK + nirS: 3.0 × 106 to 1.8 × 107; nosZ: 5.0 × 105 to 2.2 × 106 gc g soil-1). However, nitrous oxide (N2O-N) emissions (13.5 to 84.3 µg N m - 2 h - 1) and N2O export (0.014 g N) were low, and soil nitrification enzyme activities (0.45 to 1.63 mg N kg soil-1day-1) exceeded those for denitrification (0.17 to 0.49 mg N kg soil-1 day-1). Taken together, chemical, bacterial, and isotopic metrics evidenced that storm inflow NH4+sorbs and, along with mineralized soil N, nitrifies during biofilter dry-down; little denitrification and associated N2O emissions ensue, and thus subsequent storms export copious NO3--N. As such, pulsed pass-through biofilters require redesign to promote plant assimilation and/or denitrification of mineralized and nitrified N, to minimize NO3--N generation and export.

Incorporating field-based research into remote learning: An assessment of soil lead pollution in different land-use types in Los Angeles.

A research-based course was developed to investigate the legacy of soil lead (Pb) pollution in Los Angeles, California. During the course, undergraduate and graduate students collected a total of 270 soil samples for analyses of metal (loid) concentrations in different land-use types (residential, park, and school). Residential soils had significantly higher Pb concentrations than other land uses (p < 0.01) exceeding the California recommended safety level for soil Pb (80 mg/kg) at the highest frequency (64% of samples), followed by schools (42%) and parks (6.0%). Soil Pb from all 87 census block groups was correlated with battery recycling plant and railroad proximity as geospatial indicators of childhood Pb exposure risk. Meanwhile, census block groups with higher Pb levels were correlated with higher percentages of the following population: those without health insurance, without college degrees, with a lower median household income and income below the poverty line, and ethnic and racial minorities (r = -0.46 to 0.59, p < 0.05). Principal component regression models significantly improved soil Pb estimation over correlation analysis by incorporating sociodemographic, economic, and geospatial risk factors for Pb exposure (R2 = 0.58, p < 0.05). This work provides new insights into how topsoil Pb prevails in various land-use types and their co-occurring sociodemographic, economic, and geospatial risk factors, indicating the need for multi-scalar assessment across urban land uses.

Taiwan axion search experiment with haloscope: Designs and operations.

We report on a holoscope axion search experiment near 19.6 µeV from the Taiwan Axion Search Experiment with Haloscope collaboration. This experiment is carried out via a frequency-tunable cavity detector with a volume V = 0.234 liter in a magnetic field B0 = 8 T. With a signal receiver that has a system noise temperature Tsys ≅ 2.2 K and an experiment time of about one month, the search excludes values of the axion-photon coupling constant gaγγ ≳ 8.1 × 10-14 GeV-1, a factor of 11 above the Kim-Shifman-Vainshtein-Zakharov benchmark model, at the 95% confidence level in the mass range of 19.4687-19.8436 µeV. We present the experimental setup and procedures to accomplish this search.

First Results from the Taiwan Axion Search Experiment with a Haloscope at 19.6 µeV.

This Letter reports on the first results from the Taiwan Axion Search Experiment with a Haloscope, a search for axions using a microwave cavity at frequencies between 4.707 50 and 4.798 15 GHz. Apart from the nonaxion signals, no candidates with a significance of more than 3.355 were found. The experiment excludes models with the axion-two-photon coupling |g_{aγγ}|≳8.1×10^{-14} GeV^{-1}, a factor of eleven above the benchmark Kim-Shifman-Vainshtein-Zakharov model, in the mass range 19.4687

Revisiting Disulfide-Yne and Disulfide-Diazonium Reactions for Potential Direct Modification of Disulfide Bonds in Proteins.

To find their potential use in protein research, direct addition of a disulfide compound to alkyne (namely disulfide-yne reaction) and S-arylation with arenediazonium salt (namely disulfide-diazonium reaction) were investigated in aqueous or protic solutions. The reaction of dimethyl disulfide with 5-hexynol performed best under 300 nm irradiation in the presence of sodium acetate to afford 5,6-bis(methylthio)-5-hexenol in 60% yield. Without the prior reduction of a disulfide bond to thiols, the disulfide-yne reactions have the advantage of 100% atom economy. Disulfide-diazonium reaction was triggered by sodium formate and accelerated by photoirradiation with a 450 nm LED lamp (5 W). The reaction of 3,4-dihydroxy-1,2-dithiane with 2-(prop-2-yn-1-yloxy)benzene-1-diazonium tetrafluoroborate (8b) afforded 2-(benzofuran-3-yl)-1,3-dithiepane-5,6-diol (13), confirming that both S substituents originate from the same disulfide molecule. The trastuzumab antibody was incubated with diazonium 8b, followed by α-lytic protease digestion, LC-ESI-MS/MS analysis, and Mascot search, to verify that the proximal C229 and C232 residues on the same heavy chain were reconnected with a (benzofuranyl)methine moiety that originated from 8b, unlike the expected disulfide rebridging across two heavy chains. Nonetheless, disulfide-diazonium reactions still have potential for rebridging disulfide bonds if appropriate proteins and diazonium agents are chosen.

Perioperative Radiographic Predictors of Non-Union in Infra-Isthmal Femoral Shaft Fractures after Antegrade Intramedullary Nailing: A Case-Control Study.

Antegrade intramedullary (IM) nailing is the gold standard treatment for femoral shaft fractures; however, the non-union rate of infra-isthmal femoral shaft fractures is still high after antegrade IM nailing. This retrospective case−control study aimed to determine the association between perioperative radiographic factors and the non-union of infra-isthmal femoral shaft fractures after antegrade IM nailing. Univariate and multivariate analyses were used to evaluate the radiographic risk factors of non-union. Ninety-three patients were included, with thirty-one non-unions and sixty-two matched controls between 2007 and 2017. All were regularly followed up for 2 years. Receiver operating characteristic analysis revealed that a ratio of the unfixed distal segment > 32.5% was strongly predictive of postoperative non-union. The risk factors for non-union were AO/OTA type B and C (odds ratio [OR]: 2.20), a smaller ratio of the distal fragment (OR: 4.05), a greater ratio of the unfixed distal segment (OR: 7.16), a higher ratio of IM canal diameter to nail size at the level of fracture (OR: 6.23), and fewer distal locking screws (OR: 2.31). The radiographic risk factors for non-union after antegrade IM nailing for infra-isthmal femoral shaft fractures were unstable fractures, shorter distal fragments, longer unfixed distal fragments, wider IM canal, and fewer distal locking screws. Surgeons must strive to avoid non-union with longer and larger nails and apply more distal locking screws, especially for unstable, wider IM canal, and shorter distal fragment fractures.

Highly variable removal of pathogens, antibiotic resistance genes, conventional fecal indicators and human-associated fecal source markers in a pilot-scale stormwater biofilter operated under realistic stormflow conditions.

Green stormwater infrastructure systems, such as biofilters, provide many water quality and other environmental benefits, but their ability to remove human pathogens and antibiotic resistance genes (ARGs) from stormwater runoff is not well documented. In this study, a field scale biofilter in Southern California (USA) was simultaneously evaluated for the breakthrough of a conservative tracer (bromide), conventional fecal indicators, bacterial and viral human-associated fecal source markers (HF183, crAssphage, and PMMoV), ARGs, and bacterial and viral pathogens. When challenged with a 50:50 mixture of untreated sewage and stormwater (to mimic highly contaminated storm flow) the biofilter significantly removed (p < 0.05) 14 of 17 microbial markers and ARGsin descending order of concentration reduction: ermB (2.5 log(base 10) reduction) > Salmonella (2.3) > adenovirus (1.9) > coliphage (1.5) > crAssphage (1.2) > E. coli (1.0) ∼ 16S rRNA genes (1.0) ∼ fecal coliform (1.0) ∼ intl1 (1.0) > Enterococcus (0.9) ∼ MRSA (0.9) ∼ sul1 (0.9) > PMMoV (0.7) > Entero1A (0.5). No significant removal was observed for GenBac3, Campylobacter, and HF183. From the bromide data, we infer that 0.5 log-units of attenuation can be attributed to the dilution of incoming stormwater with water stored in the biofilter; removal above this threshold is presumably associated with non-conservative processes, such as physicochemical filtration, die-off, and predation. Our study documents high variability (>100-fold) in the removal of different microbial contaminants and ARGs by a field-scale stormwater biofilter operated under transient flow and raises further questions about the utility of human-associated fecal source markers as surrogates for pathogen removal.

Tracking antibiotic resistance through the environment near a biosolid spreading ground: Resistome changes, distribution, and metal(loid) co-selection.

The application of urban wastewater treatment plants (WWTPs) products to agricultural lands has contributed to the rising level of antibiotic resistance and drawn a critical public health concern. It has not been thoroughly investigated at which spatial scales a biosolid applied area as a potentially predominant source affects surrounding soil resistomes. This study investigated distribution and impact of WWTP biosolids treated with anaerobic digestion on an agricultural area. Heterotrophic plate counts (HPCs) and quantitative polymerase chain reaction (qPCR) were performed for detection of selected antibiotic-resistant bacteria (ARB), selected antibiotic resistance genes (ARGs), intI1 genes, and 16S rRNA genes. Biosolid samples contained significantly higher levels of selected ARGs than the raw agricultural soils (p < 0.05). The average relative abundances of intI1, sul1, blaSHV, and ermB genes were significantly higher in biosolid-amended soils than nearby agricultural soils (p < 0.05). Spatial interpolation analysis of relative gene abundances of intI1, sul1, sul2, and tetW across the studied area further indicated directional trends towards the northwest and southeast directions, highlighting possible airborne spread. Concentrations of Co, Cu, Ni, and Fe were found to be significantly and positively correlated with relative abundances of intI1, sul1, and tetW genes (p < 0.05). The resistance ratios of culturable antibiotic-resistant bacteria in agricultural soils with biosolid amendments were generally identical to those without biosolid amendments. This study will advance the understanding of the antibiotic resistome in agricultural soils impacted by long-term waste reuse and inform the evaluation strategies for future biosolids application and management.

Heterotopic ossification with concurrent chronic osteomyelitis of the leg following licking of a wound by a domesticated dog.

INTRODUCTION: HO with concurrent chronic osteomyelitis is extremely rare. To the authors' knowledge, this is the first case in the English-language literature with wound infection and mature HO with chronic osteomyelitis caused by mixed infection of Pasteurella canis, Peptoniphilus coxii, Peptostreptococcus canis, and Fusobacterium nucleatum following licking of a wound by a domesticated dog. CASE REPORT: A 49-year-old female with a painful, swollen, and purulent wound with bone exposure, measuring 2.5 cm × 1.5 cm, on the right leg was referred after an unsuccessful 3-month treatment regimen for an open wound resulting from a motorcycle accident. The patient's dog licked the wound several times 1 week after the accident. Sequestrectomy and debridement were performed after a 3-week OPD treatment. Postoperative treatment included NPWT applied for 6 days, 1 week of open wound care, STSG 2 weeks after the first operation, and IV antibiotics for 3 weeks. Pathologic examination was positive for HO with chronic osteomyelitis. The patient was discharged 3 weeks after admission under stable condition followed by OPD treatment. Wound healing was achieved 2 months after discharge. CONCLUSIONS: Repeated licking of the patient's wound by her dog caused the colonization of pathogens from the dog's saliva, and inappropriate wound care by the patient herself resulted in HO with chronic osteomyelitis, which was successfully treated with a regimen of NPWT, open wound care, STSG, and IV antibiotics.

Influence of soil characteristics and metal(loid)s on antibiotic resistance genes in green stormwater infrastructure in Southern California.

The synergetic effects of metal(loid)s and soil characteristics on bacterial antibiotic resistance genes (ARGs) in green stormwater infrastructure (GSI) has been relatively understudied. Surface soil samples from six GSIs in Southern California over three time periods were assessed for selected ARGs, class 1 integron-integrase genes (intI1), 16S rRNA genes, and bioavailable and total concentrations of nine metal(loid)s, to investigate the relationships among ARGs, soil characteristics, and co-occurring metal(loid)s. Significant correlations existed among relative gene abundances (sul1, sul2, tetW, and intI1), total metal(loid)s (arsenic, copper, lead, vanadium, and zinc), and bioavailable metal(loid) (arsenic) (r = 0.29-0.61, padj < 0.05). Additionally, soil texture, organic matter, and nutrients within GSI appeared to be significantly correlated with relative gene abundances of sul1, sul2, and tetW (r = -0.57 to 0.59, padj < 0.05). Multiple regression models significantly improved the estimation of ARGs in GSI when considering multiple effects of soil characteristics and metal(loid)s (r = 0.74, padj < 0.001) compared to correlation results. Total arsenic was a significant (positive) correlate in all the regression models of relative gene abundances. This work provides new insights into co-dependencies between GSI ARGs and co-occurring metal(loid)s, indicating the need for risk assessment of metal(loid)-influenced ARG proliferation.

Improvement in the Mortality-to-Incidence Ratios for Gastric Cancer in Developed Countries With High Health Expenditures.

The mortality-to-incidence ratio (MIR) is widely used to evaluate the efficacy of cancer management outcomes for individual countries. However, the association among health care expenditure, human development index (HDI), and changes in MIR over time (δMIR) remains unknown. We aimed to elucidate the significance between these indicators and gastric cancer outcomes in different countries. Among the regions, Asia had the highest number of new gastric cancer cases, gastric cancer-related deaths, age-standardized ratio of incidence, and mortality. Chile had the highest age-standardized ratio (ASR) for gastric cancer incidence and the highest ASR for mortality. Moreover, MIR was highest in Africa (0.91) and lowest in North America (0.43). Of note, MIR was negatively associated with HDI, current health expenditure (CHE) per capita, and CHE/GDP % and δMIR was positively associated with CHE/GDP % in countries with very high HDI. However, δMIR showed no significant associations with these indicators in the countries analyzed. In conclusion, increased HDI, CHE per capita, and CHE/GDP are associated with improved gastric cancer outcomes. In addition, the δMIR could be an indicator that can be used to evaluate the improvement in cancer management outcomes over time.

Limited Bacterial Removal in Full-Scale Stormwater Biofilters as Evidenced by Community Sequencing Analysis.

In urban areas, untreated stormwater runoff can pollute downstream surface waters. To intercept and treat runoff, low-impact or "green infrastructure" approaches such as using biofilters are adopted. Yet, actual biofilter pollutant removal is poorly understood; removal is often studied in laboratory columns, with variable removal of viable and culturable microbial cell numbers including pathogens. Here, to assess bacterial pollutant removal in full-scale planted biofilters, stormwater was applied, unspiked or spiked with untreated sewage, in simulated storm events under transient flow conditions, during which biofilter influents versus effluents were compared. Based on microbial biomass, sequences of bacterial community genes encoding 16S rRNA, and gene copies of the human fecal marker HF183 and of the Enterococcus spp. marker Entero1A, removal of bacterial pollutants in biofilters was limited. Dominant bacterial taxa were similar for influent versus effluent aqueous samples within each inflow treatment of either spiked or unspiked stormwater. Bacterial pollutants in soil were gradually washed out, albeit incompletely, during simulated storm flushing events. In post-storm biofilter soil cores, retained influent bacteria were concentrated in the top layers (0-10 cm), indicating that the removal of bacterial pollutants was spatially limited to surface soils. To the extent that plant-associated processes are responsible for this spatial pattern, treatment performance might be enhanced by biofilter designs that maximize influent contact with the rhizosphere.

Commercially available garden products as important sources of antibiotic resistance genes-a survey.

The dissemination of antibiotic resistance genes (ARGs) in the environment contributes to the global rise in antibiotic resistant infections. Therefore, it is of importance to further research the exposure pathways of these emerging contaminants to humans. This study explores commercially available garden products containing animal manure as a source of ARGs in a survey of 34 garden products, 3 recently landscaped soils, and 5 native soils. DNA was extracted from these soils and quantified for 5 ARGs, intI1, and 16S rRNA. This study found that both absolute and relative gene abundances in garden products ranged from approximately two to greater than four orders of magnitude higher than those observed in native soils. Garden products with Organic Materials Review Institute (OMRI) certification did not have significantly different ARG abundances. Results here indicate that garden products are important sources of ARGs to gardens, lawns, and parks.

A copper(ii)-dipicolylamine-coumarin sensor for maltosyltransferase assay.

A Cu(ii)-[di(2-methylpyridyl)methylamino]coumarin fluorescence turn-on sensor (Cu-1b) is designed to detect phosphate ions with Kass = 1.4 × 105 M-1 in HEPES buffer. Cu-1b is applied to probe the GlgE-catalyzed maltose-transfer reaction of α-maltose-1-phosphate to α-1,4-glucan with concomitant release of phosphate ions in Mycobacterium tuberculosis.

Modulating glycosylation with exogenous nucleophiles: an overview.

The major challenge in carbohydrate synthesis is stereochemical control of glycosidic bond formation. Different glycosylation methods have been developed that are based on the modulation effect of external nucleophiles. This review highlights the development, synthetic application, challenges and outlook of the modulated glycosylation methods.

Tuning reactivity of glycosyl imidinium intermediate for 2-azido-2-deoxyglycosyl donors in α-glycosidic bond formation.

The chemical properties of nucleophile additives were investigated in a modulated glycosylation context. N-Formylmorpholine (NFM) was found to be an effective modulator for glycosylation with less reactive 2-azido-2-deoxythioglucosyl and thiogalactosyl donors.

Association of a D-alanyl-D-alanine carboxypeptidase gene with the formation of aberrantly shaped cells during the induction of viable but nonculturable Vibrio parahaemolyticus.

Vibrio parahaemolyticus is a halophilic Gram-negative bacterium that causes human gastroenteritis. When the viable but nonculturable (VBNC) state of this bacterium was induced by incubation at 4°C in Morita minimal salt solution containing 0.5% NaCl, the rod-shaped cells became coccoid, and various aberrantly shaped intermediates were formed in the initial stage. This study examined the factors that influence the formation of these aberrantly shaped cells. The proportion of aberrantly shaped cells was not affected in a medium containing D-cycloserine (50 µg/ml) but was lower in a medium containing cephalosporin C (10 µg/ml) than in the control medium without antibiotics. The proportion of aberrantly shaped cells was higher in a culture medium that contained 0.5% NaCl than in culture media containing 1.0 or 1.5% NaCl. The expression of 15 of 17 selected genes associated with cell wall synthesis was enhanced, and the expression of VP2468 (dacB), which encodes D-alanyl-D-alanine carboxypeptidase, was enhanced the most. The proportion of aberrantly shaped cells was significantly lower in the dacB mutant strain than in the parent strain, but the proportion was restored in the presence of the complementary dacB gene. This study suggests that disturbance of the dynamics of cell wall synthesis by enhanced expression of the VP2468 gene is associated with the formation of aberrantly shaped cells in the initial stage of induction of VBNC V. parahaemolyticus cells under specific conditions.

Neighboring-group participation by C-2 ether functions in glycosylations directed by nitrile solvents.

Ether-protecting functions at C-2 hydroxy groups have been found to play participating roles in glycosylations when the reactions are conducted in nitrile solvent mixtures. The participation mechanism is based on intramolecular interaction between the lone electron pair of the oxygen atom of the C-2 ether function and the nitrile molecule when they are positioned in a cis configuration. A 1,2-cis glycosyl oxazolinium intermediate is formed. This participation, in conjunction with the anomeric effect of the glycosyl donor, confers high 1,2-trans selectivities on glycosylations. Further application of this concept has led to efficient preparations of α-(1→5)-arabinan oligomers.