The acidogenic fermentation of dairy wastewater (DW) was evaluated for carboxylic acids (CA) production, investigating the influence of substrate/microorganism (S/X) ratio and applying different mathematical models to the bioproduct formation data. The experiments were performed in batch reactors for 28 days, and four S/X ratios were tested (0.8, 1.2, 1.6, and 1.9 gCOD gVSS⁻¹). The S/X ratio increase did not influence the percentage of DW conversion into carboxylic acids (42–44%), but the productivity was positively affected (100–200% in general). Acetic acid was the CA formed in the highest concentration for all experiments, followed by propionic and butyric acids. Exponential models were better suited to describe this kinetics process. Therefore, according to the estimated kinetic parameters, the S/X ratio 1.6 was more suitable for CA production from acidogenic fermentation of dairy wastewater, in which the concentrations of longer CA, such as propionate and butyrate, were formed in higher quantities. In addition, it was determined a correlation between the S/X ratio and kinetic parameters like degradation/production rate constant (K) and maximum productivity rate (μₘ).

The presence of higher concentrations of heavy metals in water affects its quality with a concomitant adverse effect on its users thus their removal is paramount. A novel adsorbent, PN-Fe₃O₄-IDA derived from the chemical modification of peanut husk (a low-cost agricultural biomass produced in significant quantities globally) using magnetic nanoparticles (Fe₃O₄) and iminodiacetic acid was utilized for the remediation of heavy metals in aqueous solution. Analytical techniques vis-à-vis the Fourier-Transform Infrared, Scanning Electron Microscope, Brunauer–Emmett–Teller, X-ray photoelectron spectroscopy and X-ray Diffraction were applied for the characterization of PN-Fe₃O₄-IDA. Results from the characterization studies showed that PN-Fe₃O₄-IDA possessed a mesoporous structure, a heterogeneous surface and functional groups such as carboxylic acid and a tertiary nitrogen atom which enhanced its adsorption capacities as well as magnetic properties which ensured its easy removal from the solution using a magnet. The maximum uptake of Pb and Cu onto PN-Fe₃O₄-IDA was 0.36 and 0.75 mmol g⁻¹ (at 318 K) respectively with the chemisorption process being the major reaction pathway for the processes. The synthesized adsorbent exhibits significant adsorption capacity for the selected pollutants as well as some unique features which promotes its use as an adsorbent for wastewater remediation processes.

Pyrethroids are a class of the most commonly used insecticides. The urinary metabolites are usually used as biomarkers of pyrethroid exposures in humans. In this study, the temporal variability of urinary pyrethroid biomarkers was investigated among 114 Chinese young-aged adults who provided up to 4–11 urine samples over one year. The detection rates of four urinary pyrethroid biomarkers, 3-phenoxybenzoic acid (3PBA), 4-fluoro-3-phenoxybenzoic acid (4F-3PBA), trans-2,2-(dichloro)-2-dimethylvinylcyclopropane carboxylic acid (trans-DCCA) and cis-2,2-(dichloro)-2-dimethylvinylcyclopropane carboxylic acid (cis-DCCA) were 100%, 8%, 69% and 44%, respectively. The intraclass correlation coefficient (ICC) estimates for 3PBA indicated poor reproducibility (<0.15) in the spot urine samples of young-aged adults over a week, month and year. Log-transformed 3PBA used the least number of random spot urine samples (≥4) per person, which would provide a reliable biomarker estimate (ICC≥0.40) over a year. As the predictors of the top 33% yearly average 3PBA concentrations, the sensitivity and specificity of 3PBA ranged from 0.25 to 0.89, 0.58 to 0.96, respectively. Based on the results of this study, we recommend at least 4 urine samples collected 3 months apart for prospective assessment of pyrethroid exposure in the epidemiological studies to estimate exposure-response relationships between pyrethroids and health outcomes with relative long-term exposure periods.

Condensed organic matters (COM) with black carbon-like structures are considered as long-term carbon sinks because of their high stability. It is difficult to distinguish COM from general organic matter by conventional chemical analysis, thus the contribution by and interaction mechanisms of organo-mineral complexes in COM stabilization are unclear and generally neglected. Molecular markers related to black carbon-like structures, such as benzene polycarboxylic acids (BPCAs), are promising tools for the qualitative and quantitative analysis of COM. In this study, one natural soil and two cultivated soils with 25 y- or 55 y-tillage activities were collected and the distribution characteristics of BPCAs were detected. All the investigated soils showed similar BPCA distribution pattern, and over 60% of BPCAs were detected in clay fraction. The extractable BPCA contents were substantially increased after mineral removal. The ratios of BPCA contents before and after mineral removal indicate the extent of COM-mineral particle interactions, and our results suggested that up to 73% COM were protected by mineral particles, and more stronger interactions were noted on clay than on silt. The initial cultivation dramatically decreased COM-clay interactions, and this interaction was recovered only slowly after 55-y cultivation. Kaolinite and muscovite are important for COM protection. But a possible negative correlation between BPCAs and reactive iron oxides of the cultivated soils suggested that iron may promote COM degradation when disturbed by tillage activities. This study provided a new angle to study the stabilization of COM and emphasized the importance of organo-mineral complexes for COM stabilization.

Pyrethroids are an important class of insecticides, and thousands of tons of these compounds are used in the United States every year. This study characterized exposures to pyrethroids and assessed demographic, socioeconomic, and lifestyle factors that modulate pyrethroid exposure using data from the National Health and Nutrition Examination Survey (NHANES) 2007–2012, a nationally representative survey of the non-institutionalized population of the United States. Urinary levels of commonly used biomarkers of pyrethroid exposure, including 3-phenoxybenzoic acid (3-PBA), 4-fluoro-3-phenoxybenzoic acid (F-PBA), and cis-dibromovinyl-dimethylcyclopropane carboxylic acid (DBCA), were determined by liquid chromatography-tandem mass spectrometry. The detection rate of 3-PBA, a nonspecific metabolite of several pyrethroids, was 78.1% in adults (N = 5233) and 79.3% in children (N = 2295). The detection rates of all other pyrethroid metabolites were <10%. The median urinary level of 3-PBA in adults was 0.47 μg/L (interquartile range, 0.14–1.22 μg/L). For children, the median urinary level was 0.49 μg/L (interquartile range, 0.17–1.29 μg/L). Age, gender, family income-to-poverty ratio (PIR), levels of physical activity, alcohol intake, and body mass index were associated with 3-PBA levels in adults. In children, age, gender, race/ethnicity, and PIR were associated with 3-PBA levels. 3-PBA levels also differed significantly across NHANES cycles, with higher levels observed in NHANES 2011–2012. Geometric mean 3-PBA levels in U.S. adults were 0.41 μg/L in NHANES 2007–2008, 0.41 μg/L in NHANES 2009–2010, and 0.66 μg/L in NHANES 2011–2012. In U.S. children, geometric mean 3-PBA levels were 0.40 μg/L in NHANES 2007–2008, 0.46 μg/L in NHANES 2009–2010, and 0.70 μg/L in NHANES 2011–2012. These results demonstrate that pyrethroid exposures remain a current environmental health concern and lay the foundation for further preclinical and epidemiological studies assessing human health risks associated with pyrethroids.

The information acquired by high resolution quadrupole-time of flight mass spectrometry (QTOF-MS) allows target analysis as well as retrospective screening for the presence of suspect or unknown emerging pollutants which were not included in the target analysis. Targeted quantification of eight azole antifungal drugs in wastewater effluent as well as new and relatively simple retrospective suspect and non-target screening strategy for emerging pollutants using UHPLC-QTOF-MS is described in this work. More than 300 (parent compounds and transformation products) and 150 accurate masses were included in the retrospective suspect and non-target screening, respectively. Tentative identification of suspects and unknowns was based on accurate masses, peak intensity, blank subtraction, isotopic pattern (mSigma value), compound annotation using data bases such as KEGG and CHEBI, and fragmentation pattern interpretation. In the targeted analysis, clotrimazole, fluconazole, itraconazole, ketoconazole and posaconazole were detected in the effluent wastewater sample, fluconazole being with highest average concentration (302.38 ng L⁻¹). The retrospective screening resulted in the detection of 27 compounds that had not been included in the target analysis. The suspect compounds tentatively identified included atazanavir, citalopram, climbazole, bezafibrate estradiol, desmethylvenlafaxine, losartan carboxylic acid and cetirizine, of which citalopram, estradiol and cetirizine were confirmed using a standard. Carbamazepine, atrazine, efavirenz, lopinavir, fexofenadine and 5-methylbenzotriazole were among the compounds detected following the non-targeted screening approach, of which carbamazepine was confirmed using a standard. Given the detection of the target antifungals in the effluent, the findings are a call for a wide assessment of their occurrence in aquatic environments and their role in ecotoxicology as well as in selection of drug resistant fungi. The findings of this work further highlights the practical benefits obtained for the identification of a broader range of emerging pollutants in the environment when retrospective screening is applied to high resolution and high accuracy mass spectrometric data.

The bioaccumulative, persistent and toxic properties of long-chain perfluoroalkyl acids (PFAAs) resulted in strict regulations on PFAAs, especially in developed countries. Consequently, the industry manufacturing of PFAAs shifts from long-chain to short-chain. In order to better understand the pollution situation of PFAAs in marine environment under this new circumstance, the occurrence of 17 linear PFAAs was investigated in 30 surface seawater samples from the North Pacific to Arctic Ocean (123°E to 24°W, 32 to 82°N) during the sixth Chinese Arctic Expedition in 2014. Total concentrations of PFAAs (∑PFAAs) were between 346.9 pg per liter (pg/L) to 3045.3 pg/L. The average concentrations of ∑PFAAs decreased in the order of East China Sea (2791.4 pg/L, n = 2), Sea of Japan (East Sea) (832.8 pg/L, n = 6), Arctic Ocean (516.9 pg/L, n = 7), Chukchi Sea (505.2 pg/L, n = 4), Bering Sea (501.2 pg/L, n = 8) and Sea of Okhotsk (417.7 pg/L, n = 3). C4 to C9 perfluoroalkyl carboxylic acids (PFCAs) were detected in more than 80% of the surface water samples. Perfluorobutanoic acid (PFBA) was the most prevalent compound and perfluorooctanoic acid (PFOA) was the second abundant homolog. The concentration of individual PFAAs in the surface seawater of East China Sea was much higher than other sampling seas. As the spatial distribution of PFAAs in the marine environment was mainly influenced by the river inflow from the basin countries, which proved the large input from China. Furthermore, the marginal seas of China were found with the greatest burden of PFOA comparing the pollution level in surface seawater worldwide. PFBA concentration in the surrounding seas of China was also high, but distributed more evenly with an obvious increase in recent years. This large-scale monitoring survey will help the improvement and development of PFAAs regulations and management, where production shift should be taken into consideration.

The concentration distributions, compositional profiles and seasonal variations of 17 perfluoroalkyl acids (PFAAs) in PM₁₀ (particles with aerodynamic diameters < 10 μm) were determined in seven coastal cities of the Bohai and Yellow Seas. The detection rates of perfluorooctanoic acid (PFOA) and short-chain components (perfluoroalkyl carboxylic acids (PFCAs) with ≤7 carbon atoms and perfluoroalkane sulfonic acids (PFSAs) with ≤5 carbon atoms) were much higher than those of other long-chain PFAA species. The annual average concentration of total PFAAs in PM₁₀ ranged from 23.6 pg/m³ to 94.5 pg/m³ for the sampling cities. The monthly mean concentrations of PFAAs in PM₁₀ in some sampling cities reached a peak value in winter, while no significant seasonal differences presented in other cities. High concentrations of PFAAs in the northern cities generally occurred during the local heating period (from November to March). Generally, the dominant components of PFAAs were PFOA and perfluorobutyric acid (PFBA). Some significantly positive correlations (p < 0.01) between the 10 dominant components were revealed in the sampling cities, which implied similar sources and fate behaviors. Based on the simulated 72-hr backward trajectory tracking of air masses, the clustering results demonstrated the sampling cities were affected mainly by the atmospheric transport in sequence from the northwest, the southwest and the open seas, and many transport trajectories of air masses passed by the local fluorine chemical manufacturers in Liaoning, Shandong, Jiangsu, and Hubei Provinces. The estimated average daily intake (ADI) corresponding to the residents in different age groups indicated insignificant contributions to PFOA and perfluorooctane sulfonate (PFOS) exposures by inhalation of PM₁₀ compared to ingestion by daily diet, while the higher ADI of PFOA than the reported levels for adults should be a concern. The calculated hazard ratios (HR) exhibited low noncancer risks by inhalation exposure to PFOA and PFOS in PM₁₀.

A nationwide emission estimate of perfluoroalkyl substances (PFASs) from wastewater treatment plants (WWTPs) is required to understand the source–receptor relationship of PFASs and to manage major types of WWTPs. In this study, the concentrations of 13 PFASs (8 perfluorocarboxylic acids, 3 perfluoroalkane sulfonates, and 2 intermediates) in wastewater and sludge from 81 WWTPs in South Korea were collected. The emission pathways of PFASs were redefined, and then the national emission of PFASs from WWTPs was rigorously updated. In addition to the direct calculations, Monte Carlo simulations were also used to calculate the likely range of PFAS emissions. The total (Σ13PFAS) emission (wastewater + sludge) calculated from the direct calculation with mean concentrations was 4.03 ton/y. The emissions of perfluorooctanoic acid (PFOA, 1.19 ton/y) and perfluorooctane sulfonate (PFOS, 1.01 ton/y) were dominant. The Monte Carlo simulations suggested that the realistic national emission of Σ13PFASs is between 2 ton/y and 20 ton/y. Combined WWTPs treating municipal wastewater from residential and commercial areas were identified as a major emission source, contributing 65% to the total PFAS emissions. The Han and Nakdong Rivers were the primary contaminated rivers, receiving 89% of the total PFAS discharge from WWTPs. The results and methodologies in this study can be useful to establish a management policy for PFASs.

Per- and polyfluoroalkyl substances (PFASs) were detected in the atmosphere of a source region in Tianjin, China. Fluorotelomer alcohols (FTOHs) were the dominant neutral PFASs in the atmosphere with total concentrations of 93.6-131 pg/m3 and 8:2 FTOH contributing the most, whereas perfluorooctane sulfonamide derivatives (PFOSAs) were two magnitudes lower or undetected. In comparison, ionic PFASs (perfluoroalkyl carboxyl acids (PFCAs)) in the atmosphere were detected at similar or even higher levels. At wastewater treatment plants (WWTPs), the air over influent was found with higher levels of FTOHs than over aeration tank and effluent; whereas in the air over the aeration tank, the concentrations of PFOSAs and nonvolatile ionic PFASs substantially increased, suggesting a possible direct release of ionic PFASs to the atmosphere besides the atmospheric conversion from volatile precursors. In the air phase, a low proportion (1-5%) of PFCAs was subjected to dry deposition in the source region. Interestingly, the dry-deposition-to-bulk-air ratios of PFCA analogues were the lowest at medium chain lengths (C8 and C9) and increased with either shorter or longer chain length. The extraordinary affinity of shorter-chain PFCAs (C6-C7) to particles was presumed to be due to their smaller molecular size favoring the interactions between the carboxyl head groups and specific sorption sites on particulate matter.