Robotic YV plasty outcomes for bladder neck contracture vs. vesico-urethral anastomotic stricture.

PURPOSE: To compare the outcomes of patients undergoing robotic YV plasty for bladder neck contracture (BNC) vs. vesico-urethral anastomotic stricture (VUAS). METHODS: A retrospective study included male patients who underwent robotic YV plasty for BNC after endoscopic treatment of BPH or VUAS between August 2019 and March 2023 at a single academic center. The primary assessed was the patency rate at 1 month post-YV plasty and during the last follow-up visit. RESULTS: A total of 21 patients were analyzed, comprising 6 in the VUAS group and 15 in the BNC group. Patients with VUAS had significantly longer operative times (277.5 vs. 146.7 min; p = 0.008) and hospital stay (3.2 vs. 1.7 days; p = 0.03). Postoperative complications were more common in the VUAS group (66.7% vs. 26.7%; p = 0.14). All patients resumed spontaneous voiding postoperatively. Five patients (23.8%) who developed de novo stress urinary incontinence had already an AUS (n = 1) or required concomitant AUS implantation (n = 3), all of whom were in the VUAS group (83.3% vs. 0%; p < 0.0001). The proportion of patients improved was similar in both groups (PGII = 1 or 2: 83.3% vs. 80%; p = 0.31). Stricture recurrence occurred in 9.5% of patients in the whole cohort, with no significant difference between the groups (p = 0.50). Long-term reoperation was required in three VUAS patients, showing a statistically significant difference between the groups (p = 0.05). CONCLUSION: Robotic YV plasty is feasible for both VUAS and BNC. While functional outcomes and stricture-free survival may be similar for both conditions, the perioperative outcomes were less favorable for VUAS patients.

Risk factors for upper urinary tract deterioration in adult patients with spina bifida.

PURPOSE: Neurogenic bladder associated with spina bifida disease remains a major cause for mortality or morbidity due to kidney damages. However, we currently do not know which urodynamic findings are associated with an higher risk of upper tract damages in spina bifida patients. The objective of the present study was to evaluate urodynamic findings associated with functional kidney failure and/or with morphological kidney damages. METHODS: A large single-center restrospective study was conducted in our national referral center for spina bifida patients using our patients' files. All urodynamics curves were assessed by the same examinator. Functional and/or morphological evaluation of the upper urinary tract were done at the same moment as the urodynamic exam (between 1 week before and 1 month after). Kidney function was assessed using creatinine serum levels or 24 h urinary creatinine levels (creatinine clearance) for walking patients, or with the 24 h urinary creatinine level for wheelchair-users. RESULTS: We included 262 spina bifida patients in this study. Fifty-five patients had a poor bladder compliance (21.4%) and 88 of them had detrusor overactivity (33.6%). Twenty patients had a stage 2 kidney failure (eGFR < 60 ml/min) and 81 patients out of 254 (30.9%) had an abnormal morphological examination. There were three urodynamic findings significantly associated with UUTD: bladder compliance (OR = 0.18; p = 0.007), Pdetmax (OR = 14.7; p = 0.003) and detrusor overactivity (OR = 1.84; p = 0.03). CONCLUSION: In this large series of spina bifida patients, maximum detrusor pressure and bladder compliance are the main urodynamic findings determinants of UUTD risk.

Robot-assisted vesicovaginal fistula repair: comparison of the extravesical and transvesical techniques.

INTRODUCTION AND OBJECTIVES: Almost two decades after the description of robotic vesicovaginal fistula repair (R-VVF), the literature remains limited. The aims of this study are to report the outcomes of R-VVF and to compare the transvesical versus extravesical techniques. METHODS: We performed an observational, retrospective, multicenter study, including all patients who underwent R-VVF from March 2017 to September 2021 at four academic institutions. All abdominal VVF repair over the study period were performed using a robotic approach. The success of R-VVF was defined as the absence of clinical recurrence. The outcomes of the extravesical versus transvesical techniques were compared. RESULTS: Twenty-two patients were included. The median age was 43 years old (IQR 38-50). Fistulas were supratrigonal and trigonal in 18 and 4 cases respectively. Five patients had undergone previous attempts of fistula repair (22.7%). The fistulous tract was systematically excised, and an interposition flap was used in all but two cases (90.9%). The transvesical and extravesical techniques were used in 13 and 9 cases respectively. There were four postoperative complications, three minor and one major. None of the patients had vesicovaginal fistula recurrence after a median follow-up of 15 months. CONCLUSIONS: The present series, one of the largest R-VVF reported to date, is consistent with the few series already published with a 100% cure rate. Systematic excision of the fistulous tract and the high rate of flap interposition may explain the high success rate. The transvesical and extravesical approaches yielded similar outcomes.

Risk factors for stress urinary incontinence recurrence after midurethral sling revision.

OBJECTIVES: The purpose of this study was to report the rate of stress urinary incontinence (SUI) recurrence after sling revision, and to determine predictive factors of SUI recurrence. METHODS: We conducted a retrospective cohort study in a single academic center between 2005 and 2022, of patients who underwent sling revision. Four surgical techniques were used for sling revision (loosening, section, partial, and total excision). The primary endpoint was recurrence of SUI at 3 months postoperatively, and the other outcome of interest was the rate of subsequent anti-incontinence surgical procedure. RESULTS: Sixty-nine patients were included for analysis. SUI recurred in 46.4% of patients. Fifteen patients underwent a subsequent anti-incontinence procedure (21.8%). The time to revision was significantly longer in the group with recurrent SUI (median: 84.5 vs. 44.8 months; p = 0.004). The recurrence rate differed significantly depending on the revision technique: 7.7% after sling loosening, 22.2% after sling section, 60% after partial excision, and 66.7% after complete sling removal (p = 0.001). The risk of SUI recurrence was lower for those whose indication of reoperation was voiding dysfunction (27.3% vs. 66.7%; p = 0.002), and was higher for those who underwent a trans-obturator tap rather than a tension-free vaginal tape revision (68.4% vs. 35.7%; p = 0.02). In multivariate analysis, only the revision technique remained significantly associated with the risk of recurrence of SUI (complete excision vs. section: odds ratio = 4.66; p = 0.04). CONCLUSION: The risk of SUI recurrence may differ widely according to the techniques used, and it seems that the less extensive the surgical procedure is, the lower the risk is.

A New Surgical Technique for Female-to-Male Top Surgery: The Posterioinferior Pedicle (PIPe) Approach.

INTRODUCTION: Most of the time, female-to-male (FtoM) chest surgery involves mastectomy techniques and free transplantation of the nipple-areola complex. With the increasing prevalence of gender dysphoria and the demand for female-to-male gender reassignment surgery, the need for FtM top surgery is also rising. To meet this demand, we present a new approach: the PIPe technique, based on a fasciocutaneous flap with a posteroinferior pedicle. MATERIALS AND METHODS: All patients with FtoM gender dysphoria undergoing surgery using the posteroinferior pedicle flap technique in the Plastic Surgery Department at Rennes University Hospital Center were included. The procedure involved extensive liposuction of the lower internal and external mammary quadrants, followed by liposuction of deep tissues in the upper quadrants, except in the pedicle area. After removing skin from the lower quadrants down to the dermis and de-epithelializing the posteroinferior pedicle flap, the thoracic flap was lowered and the areola transposed. RESULTS: From July 2022 to March 2023, fifteen patients underwent surgery, and their results were collected prospectively. The average age was 25 years, the mean weight was 76.6 kg, and the average BMI was 28.1 kg/m2. The average operating time was 102 min, and the mean weight excised was 459.5 g. The average length of hospital stay was 3.3 days, and the drainage duration was 2.4 days. No major complications were reported, and there were no cases of reintervention or recurrence. CONCLUSIONS: Our study presents a novel surgical approach utilizing the posteroinferior pedicle technique. Its key benefit lies in the preservation of neurovascular function, which makes it an attractive option for patients seeking to retain nipple sensitivity. This procedure is reliable, reproducible, and recommended as a first-line treatment for grade II and III gynecomastia due to its low rate of major complications and favorable functional and aesthetic outcomes. LEVEL OF EVIDENCE IV: This journal requires that authors assign a level of evidence to each article. For a full description of these Evidence-Based Medicine ratings, please refer to the Table of Contents or the online Instructions to Authors www.springer.com/00266 .

Efficacy and safety of the TENSI+ device for posterior tibial nerve stimulation: A multicenter, retrospective study.

OBJECTIVES: Transcutaneous posterior tibial nerve stimulation (TC-PTNS) is a validated option for lower urinary tract symptoms (LUTS) management, with a short-term success rate of around 60% and few adverse events. Our goal was to report the efficacy and safety results of TC-PTNS using the newly issued device TENSI+ for LUTS management. PATIENTS AND METHODS: A multicenter, retrospective study was conducted in 7 urology departments in France. All patients treated with TC-PTNS for LUTS using the TENSI+ device between September 2021 and February 2022 were included. All patients received supervised at-home training by a specialized nurse. All patients were asked to do daily, 20minutes sessions of TC-PTNS. Patient demographics, history, initial symptoms and previous treatment were collected at inclusion. A follow-up visit was scheduled at 3 months. Efficacy was evaluated through treatment persistence at 3 months and PGI-I (Patient Global Impression of Improvement) score. Adverse events were recorded. RESULTS: One hundred and three patients (86 women and 17 men) were included. All patients had overactive bladder symptoms, 64 suffered from urgency incontinence, and 24 had associated voiding symptoms. Eighteen patients had neurogenic background, and 30 previously received anticholinergics. After a median follow-up of 12 [10-21]weeks, 70 patients were still using the device (68%). PGI-I score reflected an improvement in 70.9% and was 1, 2 and 3 in 28, 26 and 19 patients respectively, while 24 were unchanged and 6 were worse. No clinical baseline parameter was predictive of success. Adverse events included pain at stimulation site (two cases) and pelvic pain (two patients), which rapidly resolved after treatment interruption. CONCLUSIONS: TC-PTNS with TENSI+ device is an effective option for LUTS management, with results that seem similar to other TC-PTNS approaches. Adverse events were mild and reversible after treatment interruption.

Environmental photochemistry on plants: recent advances and new opportunities for interdisciplinary research.

Plants play a central role in the photochemistry of chemicals in the environment. They represent a major atmospheric source of volatile organic compounds (VOCs) but also an important environmental surface for the deposition and photochemical reactions of pesticides, gaseous and particulate pollutants. In this review, we point out the role of plant leaves in these processes, as a support affecting the reactions physically and chemically and as a partner through the release of natural constituents (water, secondary metabolites). We discuss the influence of the chosen support (leaves, needle surfaces or fruit cuticles, extracted cuticular waxes and model surfaces) and other factors (additives, pesticides mixture, and secondary metabolites) on the photochemical degradation kinetics and mechanisms. We also show how plants can be a source of photochemically reactive species which can act as photosensitizers promoting the photodegradation of pesticides or the formation and aging of secondary organic aerosols (SOA) and secondary organic materials (SOM). Understanding the fate of chemicals on plants is a research area located at the interface between photochemistry, analytical chemistry, atmospheric chemistry, microbiology and vegetal physiology. Pluridisciplinary approaches are needed to deeply understand these complex phenomena in a comprehensive way. To overcome this challenge, we summarize future research directions which have been clearly overlooked until now.

Cystectomy and ileal conduit for neurogenic bladder: Comparison of the open, laparoscopic and robotic approaches.

AIM: The objective of the present study was to compare the outcomes of open versus laparoscopic versus robotic cystectomy and ileal conduit for neurogenic lower urinary tract dysfunction (NLUTD). METHODS: The charts of all patients who underwent cystectomy and ileal conduit for NLUTD between January 2004 and November 2020 in an academic center were retrospectively reviewed. The approach was either open, laparoscopic or robot-assisted depending on the period (i.e., three consecutive era). For the robotic approach, the diversion was done either intracorporeally or extracorporeally. We compared the perioperative and late postoperative outcomes between the three groups. RESULTS: After exclusion of 10 patients with non-neurogenic benign conditions, 126 patients were included over the study period. The most frequent neurological conditions were multiple sclerosis (36.5%) and spinal cord injury (25.4%). The approach was open, laparoscopic or robot-assisted in 31 (24.6%), 26 (20.6%) and 69 (54.7%) cases respectively. Seventy-two patients experienced a 90-day postoperative complication (57.1%) of which 22 had a major complication (Clavien 3 or higher, 17.5%) including one death (0.8%). The rate of major postoperative complications was significantly lower in the robotic group (23% vs. 23% vs. 10%; p = 0.049) while the rate of overall complications was comparable across the three groups (58.1% vs. 53.9% vs. 60.6%; p = 0.84). After a median follow-up of 23 months, 22 patients presented a late complication (17.6%), mainly incisional hernia (5; 4%) and uretero-ileal stricture (9; 7.2%). The rate of late complications did not differ significantly between the three approaches. CONCLUSION: Cystectomy and ileal conduit for neurogenic bladder is associated with a relatively high perioperative morbidity. The robot-assisted approach may decrease the risk of major postoperative complications.

Phototransformation of Three Psychoactive Drugs in Presence of Sedimental Water Extractable Organic Matter.

Psychoactive drugs are classified as contaminants of emerging concern but there is limited information on their fate in surface waters. Here, we studied the photodegradation of three psychoactive drugs (sertraline, clozapine, and citalopram) in the presence of organic matter (WEOM) extracted under mild conditions from sediment of Lake Pamvotis, Greece. Spectral characterization of WEOM confirmed its humic-like nature. Preliminary experiments using chemical probes showed that WEOM was able to produce oxidant triplet excited state (3WEOM*), singlet oxygen (1O2), and hydroxyl radicals under irradiation with simulated solar light. Then, WEOM at 5 mgC L-1 was irradiated in the presence of the three drugs. It enhanced their phototransformation by a factor of 2, 4.2, and 16 for sertraline, clozapine, and citalopram, respectively. The drastic inhibiting effect of 2-propanol (5 × 10-3 M) on the reactions demonstrated that hydroxyl radical was the key intermediate responsible for drugs photodegradation. A series of photoproducts were identified by ultra-high performance liquid chromatography (UHPLC) coupled to high resolution mass spectrometry (HR-MS). The photodegradation of the three drugs proceeded through several pathways, in particular oxidations of the rings with or without O atom inclusion, N elimination, and substitution of the halogen by OH. The formation of halogenated aromatics was observed for sertraline. To conclude, sedimental natural organic matter can significantly phototransform the studied antidepressant drugs and these reactions need to be more investigated. Finally, ecotoxicity was estimated for the three target analytes and their photoproducts, using the Ecological Structure Activity Relationships (ECOSAR) computer program.

PFAS Degradation in Ultrapure and Groundwater Using Non-Thermal Plasma.

Perfluoroalkyl substances (PFAS) represent one of the most recalcitrant class of compounds of emerging concern and their removal from water is a challenging goal. In this study, we investigated the removal efficiency of three selected PFAS from water, namely, perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and pefluorooctanesulfonic acid (PFOS) using a custom-built non-thermal plasma generator. A modified full factorial design (with 2 levels, 3 variables and the central point in which both quadratic terms and interactions between couple of variables were considered) was used to investigate the effect of plasma discharge frequency, distance between the electrodes and water conductivity on treatment efficiency. Then, the plasma treatment running on optimized conditions was used to degrade PFAS at ppb level both individually and in mixture, in ultrapure and groundwater matrices. PFOS 1 ppb exhibited the best degradation reaching complete removal after 30 min of treatment in both water matrices (first order rate constant 0.107 min-1 in ultrapure water and 0.0633 min-1 in groundwater), while the degradation rate of PFOA and PFHxA was slower of around 65% and 83%, respectively. During plasma treatment, the production of reactive species in the liquid phase (hydroxyl radical, hydrogen peroxide) and in the gas phase (ozone, NOx) was investigated. Particular attention was dedicated to the nitrogen balance in solution where, following to NOx hydrolysis, total nitrogen (TN) was accumulated at the rate of up to 40 mgN L-1 h-1.

Urinary biomarkers profiles in patients with neurogenic detrusor overactivity according to their neurological condition.

OBJECTIVES: The aim of this study was to investigate the disease-specific urinary levels variations of neurotrophins (NGF, BDNF), mediators of inflammation (TGFß-1, PGE-2) and markers of extracellular matrix alterations (TIMP-2) in patients with multiple sclerosis (MS) spinal cord injury (SCI), or spina bifida (SB), and neurogenic detrusor overactivity (NDO). METHODS: A prospective single-center study was conducted between March 2015 and March 2017. Patients aged over 18 years old, with neurological disease, with a urodynamic diagnosis of NDO were included. The urinary levels of NGF, BDNF, TIMP-2, PGE 2, and TGF-ß1 were measured using dedicated ELISA kits. RESULTS: Forty-one patients were included: 6 with MS, 20 with SCI, and 15 with spina bifida. The average urinary level of NGF/Cr was significantly higher in MS patients compared to other neurologic populations (8 vs. 0.56 vs. 1.25 pg/mg of creatinine; p = 0.001) as well for the average urinary level of BDNF (88.3 vs. 5 vs. 4.8 pg/mg of creatinine; p < 0.0001). SCI patients had a significantly lower level of TGFß-1 than SB patients (p = 0.04). The urinary level of PGE2 was significantly correlated with the Body Mass Index (r = 0.61; p = 0.0002). CONCLUSION: All NDO may not be created equal from the molecular standpoint. Multiple sclerosis patients had higher urinary levels of neurotrophins than in other neurologic populations with NDO. Urinary TGFß-1, a strong determinant of extracellular matrix, was significantly higher in spina bifida patients compared to SCI patients. These findings underscore the importance of using and interpreting those possible urinary markers in a disease-specific fashion.

New Route to Toxic Nitro and Nitroso Products upon Irradiation of Micropollutant Mixtures Containing Imidacloprid: Role of NOx and Effect of Natural Organic Matter.

In this study, we reveal the capacity of imidacloprid (a neonicotinoid insecticide) to photoinduce the nitration and nitrosation of three aromatic probes (phenol, resorcinol, and tryptophan) in water. Using a gas-flow reactor and a NOx analyzer, the production of gaseous NO/NO2 was demonstrated during irradiation (300-450 nm) of imidacloprid (10-4 M). Quantum calculations showed that the formation of NOx proceeds via homolytic cleavage of the RN-NO2 bond in the triplet state. In addition to gaseous NO/NO2, nitrite and nitrate were also detected in water, with the following mass balance: 40 ± 8% for NO2, 2 ± 0.5% for NO, 52 ± 5% for NO3-, and 16 ± 2% for NO2-. The formation of nitro/nitroso probe derivatives was evidenced by high-resolution mass spectrometry, and their yields were found to range between 0.08 and 5.1%. The contribution of NO3-/NO2- to the nitration and nitrosation processes was found to be minor under our experimental conditions. In contrast, the addition of natural organic matter (NOM) significantly enhanced the yields of nitro/nitroso derivatives, likely via the production of triplet excited states (3NOM*) and HO•. These findings reveal the importance of investigating the photochemical reactivity of water contaminants in a mixture to better understand the cocktail effects on their fate and toxicity.

Risk of prolapse and urinary complications in adult spina bifida patients with neurogenic acontractile detrusor using clean intermittent catheterization versus Valsalva voiding.

AIMS: To assess the relative risks of pelvic organ prolapse (POP) and urinary complications in adult spina bifida patients with neurogenic acontractile detrusor voiding with Valsalva versus those using clean-intermittent catheterization (CIC). METHODS: We conducted a retrospective analysis including all spina bifida patients with neurogenic acontractile detrusor with a minimum follow-up of 12 months. Patients were then divided in two groups according to their bladder management: voiding with Valsalva versus CIC. The primary endpoint was any de novo or worsened rectal and/or pelvic organ prolapse (POP) diagnosed during follow-up. The secondary outcome was urinary complications defined as febrile urinary tract infections (UTI) and/or urolithiasis and/or renal failure. RESULTS: Fifty-five patients (50.9% were males) met the inclusion/exclusion criteria: 28 voiding with Valsalva and 27 performing CIC. At baseline, the rates of vaginal prolapse (44.4% vs 50%; P = 0.99), and rectal prolapse/intussusception (25.9% vs 21.4%; P = 0.76) were similar in both groups. After a median follow-up of 80.6 and 65.6 months, respectively (P = 0.29), the rate of de novo or worsened rectal prolapse/intussusception was higher in the Valsalva voiding group than in the CIC group (32.1% vs 3.7%; P = 0.01). De novo or worsened vaginal prolapses were also more common in the Valsalva voiding group, but it did not reach statistical significance (33.3% vs 11.1%; P = 0.29). CONCLUSIONS: Valsalva voiding might be harmful in adult spina bifida patients with neurogenic acontractile detrusor as it may increase the risk of rectal prolapse/intussusception. Overall, the prevalence of POP and rectal prolapse was high in both groups.

Urinary TIMP-2 and MMP-2 are significantly associated with poor bladder compliance in adult patients with spina bifida.

AIMS: To assess the predictive values of six urinary markers (nerve growth factor [NGF], brain-derived neurotrophic factor [BDNF], matrix metalloproteinase 2 [MMP-2], tissue inhibitor metalloproteinase 2 [TIMP-2], transformation growth factor ß-1 [TGF-B1], and prostaglandin 2 [PGE2]) for adverse urodynamic features and for upper urinary tract damage in adult patients with spina bifida. MATERIALS AND METHODS: A single-center prospective trial was conducted from March 2015 to March 2017 including all consecutive adult patients with spina bifida seen for urodynamic testing. The urine was collected and stored at -80°C. A urodynamic and an upper urinary tract were systematically performed. At the end of the inclusion period, urines were defrosted and urinary nerve growth factor, BDNF, TIMP-2, and TGF-B1 were assessed using validated ELISA kits. The urinary markers levels were adjusted on the urinary creatinine level. Urinary MMP-2 levels were assessed by zymography. RESULTS: Fourty patients were included. Only TIMP-2 and MMP-2 were significantly associated with poor bladder compliance (P = .043 and P = .039, respectively). TIMP-2 was also the only urinary marker significantly associated with upper urinary tract damage on imaging (OR = 19.81; P = .02). Of all urodynamic parameters, bladder compliance and maximum detrusor pressure were the only ones associated with upper urinary tract damage on imaging (P = .01 and P = .02), The diagnostic performances of urinary TIMP-2 for upper urinary tract damage were slightly superior to PdetMax and bladder compliance with an area under the curve of 0.72. CONCLUSION: Urinary TIMP-2 and MMP-2 were significantly associated with poor bladder compliance and urinary TIMP-2 was significantly associated with upper urinary tract damage. These findings support a pathophysiological role of extracellular matrix remodeling in poor bladder compliance of adult patients with spina bifida.

Phototransformation of Plastic Containing Brominated Flame Retardants: Enhanced Fragmentation and Release of Photoproducts to Water and Air.

Increasing attention is being paid to the environmental fate and impact of plastics and their additives under sunlight exposure. We evaluated the photodegradation of polystyrene (PS) films (∼100 µm) containing brominated flame retardants (BFRs): decabromodiphenylether (BDE-209), tetrabromobisphenol A (TBBPA), and tetrabromobisphenol A-bis (2.3-dibromopropylether) (TBBPA-DBPE). Irradiations were performed in a solar simulator and outdoors. Infrared (IR) analyses indicated an acceleration of the photooxidation rate of fire-retarded PS films compared to pure PS with an enhancement factor of 7 for TBBPA-DBPE and TBBPA, and 10 for BDE-209. The accelerating effect was found to be correlated with the quantum yield for BFR photodegradation and its absorbance in the PS films. The presence of BFRs also modified the PS photooxidation mechanism and resulted in the formation of 14 brominated photoproducts via bromination and oxidation of PS. Furthermore, a drastic increase in chain scissions and loss of molecular weight was revealed by size exclusion chromatography. This enhanced degradation of PS led to significant leaching (15%) of oxidation products from PS films after immersion in water, and to the gas-phase emission of several volatile brominated products. Our findings suggest that fire-retarded plastics may be a source of potentially hazardous contaminants when exposed to sunlight.

Characterization and Photodegradation of Polybrominated Diphenyl Ethers in Car Seat Fabrics from End-of-Life Vehicles.

In this study, we examined the photodegradation of decabromodiphenyl ether (BDE-209) on the surface of car seat covers from end-of-life vehicles (ELVs). Samples were collected at two car dismantling facilities in Sweden and cover car models from 1989 to 1998. The content of polybrominated diphenyl ethers (PBDEs) in nine real samples (fabric and polyurethane foam) was first characterized. Fabric samples that did not contain BDE-209 were then spiked with BDE-209 and irradiated in the laboratory and under sunlight. Photoproducts were identified using high performance liquid chromatography coupled to electrospray ionization mass spectrometer (HPLC-ESI-Orbitrap-MS), whereas volatile products were analyzed by gas chromatography-mass spectrometry (GC-MS). Similar photodegradation rates and oxidation products were observed in fabric samples irradiated in the laboratory and those collected from ELVs. Estimated half-life of BDE-209 on fabric inside vehicles ranged from 3 to 6 years. Thirteen major photoproducts were identified as lower brominated products, hydroxylated BDEs, brominated and hydroxylated dibenzofurans (PBDFs) and dioxins (PBDDs). Furthermore, several photoproducts were found to be transferable into water, particularly bromophenols and hydroxylated BDEs, and others into gas phase, such as bromomethanol and 1,2-dibromoethane. This should be taken into consideration for better estimating exposure to PBDEs and to develop strategies for ELV recycling.

Molecular Size Distribution of Fluorophores in Aquatic Natural Organic Matter: Application of HPSEC with Multi-Wavelength Absorption and Fluorescence Detection Following LPSEC-PAGE Fractionation.

Analytical high performance size exclusion liquid chromatography (HPSEC) with multiwavelength absorbance and fluorescence detections was used for the analysis of molecular size distribution and optical properties of dissolved natural organic matter. Experiments were conducted on Suwannee River organic matter (SRNOM) and its fractions A, B, C+D preliminary obtained by combination of preparative low pressure size exclusion chromatography and polyacrylamide gel electrophoresis (LPSEC-PAGE) and purified by dialysis on membrane with nominal cutoff 10 kDa, the fractions molecular size varied in order A > B > C + D > 10 kDa. The multistep fractionation of SRNOM enabled the size-separation of at least five types of humic-like fluorophores within NOM showing emission maxima at 465, 450, 435, 420, and 405 nm. The decrease of the humic-like emission maxima paralleled the decrease of the nominal molecular size of fluorescent SRNOM. The protein-like fluorescence was split into tyrosine-like and tryptophan-like fluorophores and only detected in fractions A and B. This work provides new data on the optical properties of size-fractionated NOM, which consistent with the formation of supramolecular NOM assemblies, likely controlled by association of low-molecular size components. It is clearly observed for the high molecular size fraction A, containing free amino acids or short peptides. The combination of several different fractionation procedures is very useful for obtaining less complex NOM compounds and understanding the NOM function in the environment.

Cytotoxicity on Allium cepa of the two main sulcotrione photoproducts, xanthene-1,9-dione-3,4-dihydro-6-methylsulphonyl and 2-chloro-4-mesylbenzoic acid.

The cytotoxic effects of 2-chloro-4-mesylbenzoic acid (CMBA) and xanthene-1,9-dione-3,4-dihydro-6-methylsulphonyl (XDD), the two main photoproducts of sulcotrione, were investigated on Allium root meristematic cells at different concentrations. Degradation of sulcotrione was correlated to mitotic index decrease, together with increasing anomaly and c-mitosis frequencies. Mitotic index significantly decreased with increasing XDD and CMBA concentrations. Cell frequency with abnormal chromosomes increased with CMBA or XDD application rates. In contrast, CMBA induced a low micronucleus rate even for high concentrations while XDD increased the micronucleus ratio. C-mitoses, chromosomal aberrations due to an inactivation of the spindle, were enhanced by CMBA treatments but not by XDD. The photochemical degradation process of the pesticide can change the risk for the environment.

Humic substances enhance chlorothalonil phototransformation via photoreduction and energy transfer.

The photodegradation of chlorothalonil, a polychlorinated aromatic fungicide widely used in agriculture, was investigated under ultraviolet-visible irradiation in the presence and absence of different humic substances that significantly enhance the chlorothalonil phototransformation. On the basis of a kinetic model, an analytical study, the effect of scavengers, the chlorothalonil phosphorescence measurement, and varying irradiation conditions, it was possible to demonstrate that this accelerating effect is due to their capacity to reduce the chlorothalonil triplet state via H-donor reaction and to energy transfer from the triplet humic to ground state chlorothalonil. Energy transfer occurs at wavelengths below 450 nm and accounts for up to 30% of the reaction in deoxygenated medium upon irradiation with polychromatic light (300-450 nm). This process is more important with Elliott humic and fulvic acids and with humic acids extracted from natural carbonaceous material than with Nordic NOM and Pahokee peat humic acids. The obtained results are of high relevance to understanding the processes involved in chlorothalonil phototransformation and the photoreactivity of humic substances. Chlorothalonil is one of the rare molecules shown to react by energy transfer from excited humic substances.