Biotransformation and disposition characteristics of HSK7653, a novel long-acting dipeptidyl peptidase-4 inhibitor for the treatment of type 2 diabetes.

AIM: To investigate the metabolism and disposition characteristics of HSK7653 in healthy male Chinese participants. METHODS: A single oral dose of 80 µCi (25 mg) [14C]HSK7653 capsules was administered to six healthy participants, and blood, plasma, urine and faeces were collected. Quantitative and qualitative analysis was conducted to investigate the pharmacokinetics, blood-to-plasma ratio, mass balance and metabolism of HSK7653. RESULTS: The drug was well absorbed and reached a maximum concentration at 1.25 h. The drug-related components (HSK7653 and its metabolites) were eliminated slowly, with a half-life (t1/2) of 111 h. Unchanged HSK7653 contributed to more than 97% of the total radioactivity in all plasma samples. The blood-to-plasma ratio (0.573-0.845) indicated that HSK7653 did not tend to distribute into blood cells. At 504 h postdose, up to 95.9% of the dose was excreted, including 79.8% in urine and 16.1% in faeces. Most of the radioactivity (75.5% dose) in excreta was unchanged HSK7653. In addition, nine metabolites were detected in urine and faeces. The most abundant metabolite was M6-2, a dioxidation product of HSK7653, which accounted for 4.73% and 2.63% of the dose in urine and faeces, respectively. The main metabolic pathways of HSK7653 in vivo included oxidation, pyrrole ring opening and sulphonamide hydrolysation. CONCLUSION: HSK7653 was well absorbed, slightly metabolized and slowly excreted in humans. The high plasma exposure and long t1/2 of HSK7653 may contribute to its long-lasting efficacy as a long-acting dipeptidyl peptidase-4 inhibitor.

Impact of Biotransformation on Internal Concentrations and Specificity Classification of Organic Chemicals in the Zebrafish Embryo (Danio rerio).

Internal concentrations (ICs) are crucial for linking exposure to effects in the development of New Approach Methodologies. ICs of chemicals in aquatic organisms are primarily driven by hydrophobicity and modulated by biotransformation and efflux. Comparing the predicted baseline to observed toxicity enables the estimation of effect specificity, but biological processes can lead to overestimating ICs and bias the specificity assessment. To evaluate the prediction of a mass balance model (MBM) and the impact of biotransformation on ICs, experimental ICs of 63 chemicals in zebrafish embryos were compared to predictions with physicochemical properties as input parameters. Experimental ICs of 79% (50 of 63) of the chemicals deviated less than 10-fold from predictions, and the remaining 13 deviated up to a factor of 90. Using experimental ICs changed the classification for 19 chemicals, with ICs 5 to 90 times lower than predicted, showing the bias of specificity classification. Uptake kinetics of pirinixic acid, genistein, dexamethasone, ethoprophos, atorvastatin, and niflumic acid were studied over a 96 h exposure period, and transformation products (TPs) were elucidated using suspect- and nontarget screening with UPLC-HRMS. 35 TPs (5 to 8 TPs per compound) were tentatively identified and semiquantified based on peak areas, suggesting that biotransformation may partly account for the overpredictions of ICs.

Combining Advanced Analytical Methodologies to Uncover Suspect PFAS and Fluorinated Pharmaceutical Contributions to Extractable Organic Fluorine in Human Serum (Tromsø Study).

A growing number of studies have reported that routinely monitored per- and polyfluoroalkyl substances (PFAS) are not sufficient to explain the extractable organic fluorine (EOF) measured in human blood. In this study, we address this gap by screening pooled human serum collected over 3 decades (1986-2015) in Tromsø (Norway) for >5000 PFAS and >300 fluorinated pharmaceuticals. We combined multiple analytical techniques (direct infusion Fourier transform ion cyclotron resonance mass spectrometry, liquid chromatography-Orbitrap-high-resolution mass spectrometry, and total oxidizable precursors assay) in a three-step suspect screening process which aimed at unequivocal suspect identification. This approach uncovered the presence of one PFAS and eight fluorinated pharmaceuticals (including some metabolites) in human serum. While the PFAS suspect only accounted for 2-4% of the EOF, fluorinated pharmaceuticals accounted for 0-63% of the EOF, and their contribution increased in recent years. Although fluorinated pharmaceuticals often contain only 1-3 fluorine atoms, our results indicate that they can contribute significantly to the EOF. Indeed, the contribution from fluorinated pharmaceuticals allowed us to close the organofluorine mass balance in pooled serum from 2015, indicating a good understanding of organofluorine compounds in humans. However, a portion of the EOF in human serum from 1986 and 2007 still remained unexplained.

ICP-MS As a Contributing Tool to Nontarget Screening (NTS) Analysis for Environmental Monitoring.

Due to the increasing number of chemicals released into the environment, nontarget screening (NTS) analysis is a necessary tool for providing comprehensive chemical analysis of environmental pollutants. However, NTS workflows encounter challenges in detecting both known and unknown pollutants with common chromatography high-resolution mass spectrometry (HRMS) methods. Identification of unknowns is hindered by limited elemental composition information, and quantification without identical reference standards is prone to errors. To address these issues, we propose the use of inductively coupled plasma mass spectrometry (ICP-MS) as an element-specific detector. ICP-MS can enhance the confidence of compound identification and improve quantification in NTS due to its element-specific response and unambiguous chemical composition information. Additionally, mass balance calculations for individual elements (F, Br, Cl, etc.) enable assessment of total recovery of those elements and evaluation of NTS workflows. Despite its benefits, implementing ICP-MS in NTS analysis and environmental regulation requires overcoming certain shortcomings and challenges, which are discussed herein.

Development of a certified reference material for D-phenylalanine with evaluation of enantiomeric purity.

D-Phenylalanine (D-Phe) is a small chiral organic molecule that is both an important pharmaceutical intermediate and used as a calibrator for quantifying amino acids in liquid chromatography-circular dichroism. We have developed a process for a national certified reference material (CRM) for D-Phe following ISO 17034:2016. The identity of D-Phe was confirmed using mass spectrometry (MS) and nuclear magnetic resonance (NMR), infrared, and ultraviolet (UV) spectroscopy. The absolute optical conformation was also determined using circular dichroism (CD) spectroscopy and optical rotation measurements. Impurities were identified via liquid chromatography (LC) with a UV-Vis detector and a charged aerosol detector (CAD) and LC-MS. Both mass balance and quantitative NMR were employed for value assessment, and the associated uncertainty was evaluated. The certified purity was determined to be 0.995 ± 0.003 g/g, a validation that was confirmed by CD using L-Phe CRM as a calibrator. Twenty milligrams of raw material was packed in sealed brown glass tubes for storage, and no inhomogeneity was observed. Stability tests revealed that the D-Phe CRM remained stable at -20 °C for at least 26 months, at 4 °C for at least 14 days, and at 25 °C and 60 °C for at least 7 days. The D-Phe CRM can be used to ensure the accuracy and reliability of D-Phe quantitation in the pharmaceutical field and also as a calibrator to ensure traceability to the International System of Units (SI) for L-Phe quantitation and protein purity analysis using LC-CD methods. The approach outlined in this paper also has potential for use in the development of other chiral CRMs.

Fate of antibiotics and hormones during hydrothermal carbonization of poultry litter: degradation kinetics and toxicity assessment of filtrates and hydrochars.

This study investigated degradation kinetics of five selected organic micropollutants (OMPs) present in poultry litter (namely: sulfadiazine, tetracycline, and doxycycline hyclate (antibiotics); estrone and 17-ß-estradiol (hormones)) during hydrothermal carbonization (HTC) treatment as the temperature stepwise increased to 250 °C. All five pure OMPs were completely degraded before 250 °C was reached during the HTC process. Nevertheless, presence of poultry litter slowed down the degradation of OMPs. Through elemental mass balance calculation, it is noted that after 15 min (temperature less than 137 °C), 69-82% of organic carbon and 50-66% of organic nitrogen initially consisting part of the target antibiotics were fully mineralized. Both HTC filtrates and hydrochars obtained from poultry litter inhibited Escherichia coli and Bacillus subtilis growth. A combination of high salinity, high nutrients, dissolved organic carbon, and other ions in the filtrate as well as the adsorption of OMPs on hydrochars were probably the reason for the high toxicity.

Fate of contaminants of emerging concern in two wastewater treatment plants after retrofitting tertiary treatment for reduction of nitrogen discharge.

More and more previously designed wastewater treatment plants (WWTPs) are upgraded to tertiary treatment to meet the higher effluent discharge standards of conventional pollutants. Contaminants of emerging concern (CECs) can cause adverse effects on organisms and usually flow into WWTPs along with urban sewage. How the retrofitted WWTPs targeting conventional pollutants will influence the treatment efficiency of CECs is seldom discussed. This study investigates the removal of CECs in two full-scale newly retrofitted WWTPs (CD and JM WWTPs), containing high-efficiency sedimentation tank and denitrification deep bed filter for enhancing total nitrogen removal. The overall CEC removal efficiencies in the CD and JM WWTPs were 73.79 % and 93.63 %, respectively. Mass balance results indicated that CD WWTP and JM WWTP release a total of 36.89 and 88.58 g/d of CECs into the environment through effluent and excess sludge, respectively. Analysis of the concentration of CECs along the treatment process revealed most CECs were removed in the biological treatment units. The incorporation of newly constructed tertiary treatment proved beneficial for CEC removal and removed 2.93 % and 2.36 % CECs, corresponding to CEC removal of 2.92 and 27.49 g/d in the CD and JM WWTPs, respectively. The data of this study were further used to evaluate the suitability of the SimpleTreat model for simulating the fate of CECs in WWTPs. The predicted fraction of CECs discharged through the biological treatment effluent were generally within ten-fold difference from the measured results, highlighting its potential for estimating CEC removal in WWTPs.

Sampling from Extracorporeal Circuit: A Step Forward for Dose Monitoring in Continuous Renal Replacement Therapy.

INTRODUCTION: Continuous renal replacement therapies (CRRTs) require constant monitoring and periodic treatment readjustments, being applied to highly complex patients, with rapidly changing clinical needs. To promote precision medicine in the field of renal replacement therapy and encourage dynamic prescription, the Acute Dialysis Quality Initiative (ADQI) recommends periodically measuring the solutes extracorporeal clearance with the aim of assessing the current treatment delivery and the gap from the therapeutic prescription (often intended as effluent dose). To perform this procedure, it is therefore necessary to obtain blood and effluent samples from the extracorporeal circuit to measure the concentrations of a target solute (usually represented by urea) in prefilter, postfilter, and effluent lines. However, samples must be collected simultaneously from the extracorporeal circuit ports, with the same suction flow at an unknown rate. METHODS: The proposed study takes the first step toward identifying the technical factors that should be considered in determining the optimal suction rate to collect samples from the extracorporeal circuit to measure the extracorporeal clearance for a specific solute. RESULTS: The results obtained identify the low suction rate (i.e., 1 mL/min) as an ideal parameter for an adequate sampling method. Low velocities do not perturb the external circulation system and ensure stability prevailing pressures in the circuit. Higher velocities can be performed only with blood flows above 120 mL/min preferably in conditions of appropriate filtration fraction. DISCUSSION/CONCLUSIONS: The specific value of aspiration flow rate must be proportioned to the prescription of CRRT treatments set by the clinician.

Previously unaccounted atmospheric mercury deposition in a midlatitude deciduous forest.

Mercury is toxic to wildlife and humans, and forests are thought to be a globally important sink for gaseous elemental mercury (GEM) deposition from the atmosphere. Yet there are currently no annual GEM deposition measurements over rural forests. Here we present measurements of ecosystem-atmosphere GEM exchange using tower-based micrometeorological methods in a midlatitude hardwood forest. We measured an annual GEM deposition of 25.1 µg ⋅ m-2 (95% CI: 23.2 to 26.7 1 µg ⋅ m-2), which is five times larger than wet deposition of mercury from the atmosphere. Our observed annual GEM deposition accounts for 76% of total atmospheric mercury deposition and also is three times greater than litterfall mercury deposition, which has previously been used as a proxy measure for GEM deposition in forests. Plant GEM uptake is the dominant driver for ecosystem GEM deposition based on seasonal and diel dynamics that show the forest GEM sink to be largest during active vegetation growing periods and middays, analogous to photosynthetic carbon dioxide assimilation. Soils and litter on the forest floor are additional GEM sinks throughout the year. Our study suggests that mercury loading to this forest was underestimated by a factor of about two and that global forests may constitute a much larger global GEM sink than currently proposed. The larger than anticipated forest GEM sink may explain the high mercury loads observed in soils across rural forests, which impair water quality and aquatic biota via watershed Hg export.

Seasonal patterns, fate and ecological risk assessment of pharmaceutical compounds in a wastewater treatment plant with Bacillus bio-reactor treatment.

Pharmaceutical compounds (PhCs) pose a growing concern with potential environmental impacts, commonly introduced into the environment via wastewater treatment plants (WWTPs). The occurrence, removal, and season variations of 60 different classes of PhCs were investigated in the baffled bioreactor (BBR) wastewater treatment process during summer and winter. The concentrations of 60 PhCs were 3400 ± 1600 ng/L in the influent, 2700 ± 930 ng/L in the effluent, and 2400 ± 120 ng/g dw in sludge. Valsartan (Val, 1800 ng/L) was the main contaminant found in the influent, declining to 520 ng/L in the effluent. The grit chamber and BBR tank were substantially conducive to the removal of VAL. Nonetheless, the BBR process showcased variable removal efficiencies across different PhC classes. Sulfadimidine had the highest removal efficiency of 87 ± 17% in the final effluent (water plus solid phase). Contrasting seasonal patterns were observed among PhC classes within BBR process units. The concentrations of many PhCs were higher in summer than in winter, while some macrolide antibiotics exhibited opposing seasonal fluctuations. A thorough mass balance analysis revealed quinolone and sulfonamide antibiotics were primarily eliminated through degradation and transformation in the BBR process. Conversely, 40.2 g/d of macrolide antibiotics was released to the natural aquatic environment via effluent discharge. Gastric acid and anticoagulants, as well as cardiovascular PhCs, primarily experienced removal through sludge adsorption. This study provides valuable insights into the intricate dynamics of PhCs in wastewater treatment, emphasizing the need for tailored strategies to effectively mitigate their release and potential environmental risks.

Purity Assessment of Tripropyl Phosphate through Mass Balance and 1H and 31P Quantitative Nuclear Magnetic Resonance.

Tripropyl phosphate (TnPP) is a commonly used organic phosphate flame retardant in the textiles, plastics, and coating industries. Residues are commonly detected in samples from the environment and food. The availability of certified reference materials (CRMs) is essential to ensure the accuracy and traceability of detection results. In this study, a comprehensive characterization of a CRM for TnPP was carried out, and its purity was evaluated using two distinct methodologies: mass balance (MB) and quantitative nuclear magnetic resonance spectroscopy (qNMR). In the MB method, the levels of structurally related organic impurities are 1.37 mg/g. The water content was determined to be 3.16 mg/g, while inorganic impurities were found to be 0.87 mg/g, and no residual organic solvents were detected. Benzoic acid and monocrotophos were chosen as internal standards for 1H-qNMR and 31P-qNMR, respectively. The purity of the TnPP CRM was assessed as 994.6 mg/g, 994.1 mg/g, and 993.5 mg/g using MB, 1H-qNMR, and 31P-qNMR techniques, respectively. The verified purity of the TnPP CRM was ultimately determined to be 994.1 mg/g, with an expanded uncertainty of 3.4 mg/g (k = 2), ensuring traceability to the International System of Units (SI). This CRM can be effectively utilized for preparing calibration solutions suitable for the routine monitoring of TnPP residues in plastics and food samples.

Axenic green microalgae for the treatment of textile effluent and the production of biofuel: a promising sustainable approach.

An integrated approach to nutrient recycling utilizing microalgae could provide feasible solutions for both environmental control and energy production. In this study, an axenic microalgae strain, Chlorella sorokiniana ASK25 was evaluated for its potential as a biofuel feedstock and textile wastewater (TWW) treatment. The microalgae isolate was grown on TWW supplemented with different proportions of standard BG-11 medium varying from 0 to 100% (v/v). The results showed that TWW supplemented with 20% (v/v) BG11 medium demonstrated promising results in terms of Chlorella sorokiniana ASK25 biomass (3.80 g L-1), lipid production (1.24 g L-1), nutrients (N/P, > 99%) and pollutant removal (chemical oxygen demand (COD), 99.05%). The COD level dropped by 90% after 4 days of cultivation, from 2,593.33 mg L-1 to 215 mg L-1; however, after day 6, the nitrogen (-NO3-1) and total phosphorus (TP) levels were reduced by more than 95%. The biomass-, total lipid- and carbohydrate- production, after 6 days of cultivation were 3.80 g L-1, 1.24 g L-1, and 1.09 g L-1, respectively, which were 2.15-, 2.95- and 3.30-fold higher than Chlorella sorokiniana ASK25 grown in standard BG-11 medium (control). In addition, as per the theoretical mass balances, 1 tonne biomass of Chlorella sorokiniana ASK25 might yield 294.5 kg of biodiesel and 135.7 kg of bioethanol. Palmitic acid, stearic acid, and oleic acid were the dominant fatty acids found in the Chlorella sorokiniana ASK25 lipid. This study illustrates the potential use of TWW as a microalgae feedstock with reduced nutrient supplementation (20% of TWW). Thus, it can be considered a promising feedstock for economical biofuel production.

Remote sensing monitoring of glacier area and volume changes in glacier-fed mountainous watershed on the Northern margin of the Qinghai-Tibet Plateau under climate change.

Steady glacier runoff is related to the security and resilience of water resources in meltwater recharge basins, so the status and change of glaciers and their response to climate change in the upper reaches have received widespread concerns. Here, the spatiotemporal characteristics of glacier wastage in the Upper Reaches of Shule River Basin (URSRB) driven by climate change were analyzed based on multi-source and multi-temporal remotely sensed images. Firstly, we extracted multi-temporal glacier outlines from the Landsat time series data using Google Earth Engine (GEE) for seven different periods every approximately 5 years from 1990 to 2020. The spatiotemporal analysis of URSRB glaciers demonstrates a sustained reduction in glacier area from 481.07 ± 24.24 km2 in 1990 to 384.05 ± 22.71 km2 in 2020, corresponding to a glacier shrinkage rate of - 0.67 ± 0.23%/year, characterized by considerable temporal variability. Secondly, multi-temporal DEMs derived from ASTER stereo imagery spanning from 2000 to 2020 were used to compute the glacier surface elevation changes and determine the glacier mass loss. The overall glacier surface elevation change rate was - 0.32 ± 0.14 m/year, equivalent to a mass balance of - 0.28 ± 0.12 m w.e./year. Lastly, to better apprehend the long-term response of URSRB glaciers to climate change, studies on climate change were carried out based on the EAR5-Land reanalysis dataset. The long-term trend of glacier wastage is attributed to the increase in summer temperature, and the negative effects of increased summer temperature on glaciers exceeded the positive effects of increased annual precipitation. In summary, glaciers in the URSRB have experienced a significant area reduction and accelerated mass loss against the backdrop of climatic warming and humidification.

Absorption, Metabolism, and Excretion of [14C]-Tebipenem Pivoxil Hydrobromide (TBP-PI-HBr) in Healthy Male Subjects.

Tebipenem pivoxil hydrobromide (TBP-PI-HBr) is an oral prodrug of pharmacologically active moiety tebipenem (TBP), which is a carbapenem with activity against multidrug-resistant Gram-negative pathogens. Conversion from the prodrug to the active moiety, namely, TBP, occurs in the enterocytes of the gastrointestinal tract via intestinal esterases. The absorption, metabolism, and excretion in humans were evaluated, following the administration of a single oral dose of [14C]-TBP-PI-HBr. Healthy male subjects (n = 8) received a single 600 mg oral dose of TBP-PI-HBr containing approximately 150 µCi of [14C]-TBP-PI-HBr. Blood, urine, and fecal samples were collected to determine the total radioactivity, concentrations of TBP (plasma only), and metabolite profiling and identification. The overall mean recovery of the total radioactivity in urine (38.7%) and feces (44.6%) combined was approximately 83.3% of the administered dose, with individual recoveries ranging from 80.1% to 85.0%. Plasma TBP LC-MS/MS and metabolite profiling data suggest that TBP was the main circulating component in plasma and that it accounts for approximately 54% of the total plasma radioactivity, based on the plasma AUC ratio of TBP/total radioactivity. The ring-open metabolite LJC 11562 was another major component in plasma (>10%). TBP (M12), LJC 11562, and four trace to minor metabolites were identified/characterized in the urine. TBP-PI, TBP (M12), and 11 trace to minor metabolites were identified/characterized in the feces. The renal and fecal routes are major clearance pathways in the elimination of [14C]-TBP-PI-HBr, with a mean combined recovery of 83.3%. TBP and its inactive ring-open metabolite LJC 11562 were the major circulating metabolites in the plasma.

A phase 1 study to investigate the absorption, distribution, metabolism and excretion of brepocitinib in healthy males using a 14 C-microdose approach.

AIMS: Brepocitinib is a tyrosine kinase 2/Janus kinase 1 inhibitor being investigated for the treatment of several autoimmune diseases. This study assessed the absorption, distribution, metabolism and excretion of oral brepocitinib, and the absolute oral bioavailability (F) and fraction absorbed (Fa ) using a 14 C microtracer approach. METHODS: This was a phase 1 open-label, nonrandomized, fixed sequence, two-period, single-dose study of brepocitinib in healthy male participants. Participants received a single oral 60 mg dose of 14 C brepocitinib (~300 nCi) in Period A, then an unlabelled oral 60 mg dose followed by an intravenous (IV) 30 µg dose of 14 C labelled brepocitinib (~300 nCi) in Period B. Mass balance, pharmacokinetic parameters and safety were assessed. RESULTS: Six participants were enrolled. Brepocitinib was absorbed rapidly following oral administration. In Period A, total recovery of the oral dose was 96.7% ± 6.3% (88.0% ± 8.0% in urine, 8.7% ± 2.1% in faeces). In Period B, a small fraction (6.0% of the oral dose) was recovered unchanged in urine. F and Fa were 74.6% (90% confidence interval 67.3%, 82.8%) and 106.9%, respectively. Brepocitinib demonstrated an acceptable safety profile and was well tolerated following oral or oral then IV administrations. No deaths, serious adverse events or discontinuations were reported. CONCLUSION: Intestinal absorption of brepocitinib was essentially complete after oral administration, with F ~75%. Drug-related material recovery was high, with the majority excreted in urine. The major route of elimination of brepocitinib was renal excretion as metabolites, whereas urinary elimination of unchanged brepocitinib was minor. NCT: NCT03770039.

Evaluation of the drug disposition of RO7049389 with in vitro data and human mass balance supported by physiologically based pharmacokinetic modelling.

AIMS: RO7049389 (linvencorvir) is a developmental oral treatment for chronic hepatitis B virus infection. The aim of this work was to conduct mass balance (MB) and absolute bioavailability (BA) analyses in healthy volunteers, alongside in vitro evaluations of the metabolism of RO7049389 and a major circulating active metabolite M5 in human hepatocytes, and physiologically based pharmacokinetic (PBPK) modelling to refine the underlying drug disposition paradigm. METHODS: Participants in the clinical study (MB: Caucasian, male, n = 6; BA: Caucasian and Asian, male and female, n = 16, 8 in each ethnic groups) received oral [14 C] or unlabelled RO7049389 (600/1000 mg) followed by 100 µg intravenous [13 C]RO7049389. Metabolic pathways with fractions metabolized-obtained from the in vitro incubation results of 10 µM [14 C]RO7049389 and 1 µM M5 with (long-term cocultured) human hepatocytes in the absence and presence of the cytochrome P450 3A4 (CYP3A4) inhibitor itraconazole-were used to complement the PBPK models, alongside the clinical MB and BA data. RESULTS: The model performance in predicting the pharmacokinetic profiles of RO7049389 and M5 aligned with clinical observations in Caucasians and was also successfully applied to Asians. Accordingly, the drug disposition pathways for RO7049389 were postulated with newly characterized estimates of the fractions: biliary excretion by P-glycoprotein (~41%), direct glucuronidation via uridine 5'-diphosphoglucuronosyltransferase 1A3 (~11%), hexose conjugation (~6%), oxidation by CYP3A4 (~28%) and other oxidation reactions (~9%). CONCLUSION: These results support the ongoing clinical development program for RO7049389 and highlight the broader value of PBPK and MB analyses in drug development.

Accounting of the Use and Emissions of Polychlorinated Biphenyl Compounds (PCBs) in India, 1951-2100.

Polychlorinated biphenyl compounds (PCBs) are highly toxic organic chemicals still prevalent in the environment. While global inventories of the use and emissions of PCBs have been developed, estimates for individual countries determined using bottom-up approaches are few and often show different trends from the global inventory. Here, we determine the past, present, and future consumption and emissions of PCBs in India. A mass balance model was used to estimate middle (low-high) emissions in the period 1950-2100. Up to 7296 tonnes of PCBs have been used in transformers. PCBs imported as wastes are estimated to be approximately 5000 (2400-9100) tonnes. Total emissions from the use and disposal of transformers, industrial processes, and imported waste disposal are estimated to become 13 (0.1-537) tonnes, 89.26 (0.5-178) tonnes, 63 (3-910) tonnes, respectively, in the period 1950-2100. Congener-specific emissions are relatively high for low-chlorinated PCBs (-8, 18, 28, 31, 52, 101, 110, 118, 153, range: 0.1-118 tonnes). We find that industrial emissions are becoming important sources of PCBs and may become predominant, depending on emission scenarios.

Occurrence and Fate of Substituted p-Phenylenediamine-Derived Quinones in Hong Kong Wastewater Treatment Plants.

para-Phenylenediamine quinones (PPD-Qs) are a newly discovered class of transformation products derived from para-phenylenediamine (PPD) antioxidants. These compounds are prevalent in runoff, roadside soil, and particulate matter. One compound among these, N-1,3-dimethylbutyl-n'-phenyl-p-phenylenediamine quinone (6PPD-Q), was found to induce acute mortality of coho salmon, rainbow trout, and brook trout, with the median lethal concentrations even lower than its appearance in the surface and receiving water system. However, there was limited knowledge about the occurrence and fate of these emerging environmental contaminants in wastewater treatment plants (WWTPs), which is crucial for effective pollutant removal via municipal wastewater networks. In the current study, we performed a comprehensive investigation of a suite of PPD-Qs along with their parent compounds across the influent, effluent, and biosolids during each processing unit in four typical WWTPs in Hong Kong. The total concentrations of PPDs and PPD-Qs in the influent were determined to be 2.7-90 and 14-830 ng/L. In the effluent, their concentrations decreased to 0.59-40 and 2.8-140 ng/L, respectively. The median removal efficiency for PPD-Qs varied between 53.0 and 91.0% across the WWTPs, indicating that a considerable proportion of these contaminants may not be fully eliminated through the current processing technology. Mass flow analyses revealed that relatively higher levels of PPD-Qs were retained in the sewage sludge (20.0%) rather than in the wastewater (16.9%). In comparison to PPDs, PPD-Qs with higher half-lives exhibited higher release levels via effluent wastewater, which raises particular concerns about their environmental consequences to aquatic ecosystems.

Deposition and Re-Emission of Atmospheric Elemental Mercury over the Tropical Forest Floor.

Significant knowledge gaps exist regarding the emission of elemental mercury (Hg0) from the tropical forest floor, which limit our understanding of the Hg mass budget in forest ecosystems. In this study, biogeochemical processes of Hg0 deposition to and evasion from soil in a Chinese tropical rainforest were investigated using Hg stable isotopic techniques. Our results showed a mean air-soil flux as deposition of -4.5 ± 2.1 ng m-2 h-1 in the dry season and as emission of +7.4 ± 1.2 ng m-2 h-1 in the rainy season. Hg re-emission, i.e., soil legacy Hg evasion, induces negative transitions of Δ199Hg and δ202Hg in the evaded Hg0 vapor, while direct atmospheric Hg0 deposition does not exhibit isotopic fractionation. Using an isotopic mass balance model, direct atmospheric Hg0 deposition to soil was estimated to be 48.6 ± 13.0 µg m-2 year-1. Soil Hg0 re-emission was estimated to be 69.5 ± 10.6 µg m-2 year-1, of which 63.0 ± 9.3 µg m-2 year-1 is from surface soil evasion and 6.5 ± 5.0 µg m-2 year-1 from soil pore gas diffusion. Combined with litterfall Hg deposition (∼34 µg m-2 year-1), we estimated a ∼12.6 µg m-2 year-1 net Hg0 sink in the tropical forest. The fast nutrient cycles in the tropical rainforests lead to a strong Hg0 re-emission and therefore a relatively weaker atmospheric Hg0 sink.

Muddied Waters: The Use of "Residual" And "Legacy" Phosphorus.

Phosphorus (P) inputs to the biosphere have quadrupled in less than a century due to intensification of rock phosphate mining and the use of P fertilizers for crop production. Accumulation of P in soils can increase P transfers across the soil-water continuum that impair aquatic ecosystem function and water resource quality for society. However, what this accumulated P is called, and subsequent connotations of magnitude versus mechanism at pedon versus watershed scale, varies in the literature. We argue that the two commonly used terms of "residual" and "legacy" P, though often used interchangeably, hold distinct meanings and connotations. Tracing the historical origins and trajectories of these terms reveals that "residual P" refers to the magnitude of fertilizer P that remains in the soil after crop harvest, whereas "legacy P" refers to the mechanism of P transfer across the watershed and its long-term impacts on water quality. The use of "legacy P" in many cases refers to the residuality of anthropogenic P inputs, and thus should be "residual P". We recommend that the term "residual P" be used when referring to the accumulation of P in soils under agricultural management from past inputs, and the term "legacy P" be used when referring to the transfer of P within watersheds. The intentional and thus consistent use of residual versus legacy P stands to provide important nuance in the environmental sciences and overlapping fields of agronomy and biogeochemistry.