Analysing N-nitrosamine occurrence and sources in karst reservoirs, Southwest China.

N-nitrosamines in reservoir water have drawn significant attention because of their carcinogenic properties. Karst reservoirs containing dissolved organic matter (DOM) are important drinking water sources and are susceptible to contamination because of the fast flow of various contaminants. However, it remains unclear whether N-nitrosamines and their precursor, DOM, spread in karst reservoirs. Therefore, this study quantitatively investigated the occurrence and sources of N-nitrosamines based on DOM properties in three typical karst reservoirs and their corresponding tap water. The results showed that N-nitrosamines were widely spread, with detection frequencies > 85%. Similar dominant compounds, including N-nitrosodimethylamine, N-nitrosomethylethylamine, N-nitrosopyrrolidine, and N-nitrosodibutylamine, were observed in reservoirs and tap water, with average concentrations of 4.7-8.9 and 2.8-6.7 ng/L, respectively. The average carcinogenic risks caused by these N-nitrosamines were higher than the risk level of 10-6. Three-dimensional fluorescence excitation-emission matrix modeling revealed that DOM was composed of humus-like component 1 (C1) and protein-like component 2 (C2). Fluorescence indicators showed that DOM in reservoir water was mainly affected by exogenous pollution and algal growth, whereas in tap water, DOM was mainly affected by microbial growth with strong autopoietic properties. In the reservoir water, N-nitrosodiethylamine and N-nitrosopiperidine were significantly correlated with C2 and biological indicators, indicating their endogenously generated sources. Based on the principal component analysis and multiple linear regression methods, five sources of N-nitrosamines were identified: agricultural pollution, microbial sources, humus sources, degradation processes, and other factors, accounting for 46.8%, 36.1%, 7.82%, 8.26%, and 0.96%, respectively. For tap water, two sources, biological reaction processes, and water distribution systems, were identified, accounting for 75.7% and 24.3%, respectively. Overall, this study presents quantitative information on N-nitrosamines' sources based on DOM properties in typical karst reservoirs and tap water, providing a basis for the safety of drinking water for consumers.

Synergistic removal performance and mechanism of Cd(II) and As(III) from irrigation water by iron sulfide-based porous biochar.

Since Cd(II) and As(III) have extremely opposite chemical characteristics, it is a huge challenging to simultaneously remove these two ions from aqueous solutions. Therefore, a novel iron sulfide-based porous biochar (FSB) was synthesized and used to evaluate its Cd(II) and As(III) removal performance and mechanisms. The characterization and batch experiments results indicated that FeS was successfully loaded on the surface of biochar and increased its adsorption sites. The iron sulfide-based porous biochar was very favorable for the removal of Cd(II) and As(III) in the weakly acidic environment. The maximum adsorption of Cd(II) and As(III) by FSB was 108.8 mg g-1 and 76.3 mg g-1, respectively, according to the Langmuir and Freundlich isothermal adsorption model, and the adsorption equilibrium time was 12 h and 4 h, respectively, according to the pseudo-second-order kinetic model. In the coexisting ion system, Cd(II) adsorption was suppressed by Ca2+, Mg2+, and humic acid, but enhanced by PO43- and As(III). As(III) adsorption was inhibited by PO43- and humic acid. Precipitation and complexation are the predominant adsorption mechanisms of Cd(II) and As(III), which contribute to the formation of Cd-O, Fe-O-Cd, As-O, Fe-O-As, ternary complex Cd-Fe-As, and stable compounds FeAsO4·2H2O and CdS. Therefore, The iron sulfide-based porous biochar can be an efficient and environmentally friendly candidate for the treatment of Cd(II) and As(III) co-polluted irrigation water.

Impact of agricultural activities on the occurrence of N-nitrosamines in an aquatic environment.

N-Nitrosamines, nitroso compounds with strong carcinogenic effects on humans, have been frequently detected in natural waters. In agricultural areas, there is typically a lack of drinking water treatment processes and distribution systems. As a result, residents often consume groundwater as drinking water which may contain N-nitrosamines, necessitating the investigation of the occurrence, sources, and carcinogenic risk of N-nitrosamines within the groundwater of agricultural areas. This study identified eight N-nitrosamines in groundwater and river water in the Jianghan Plain, a famous agricultural region in central China. N-Nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosomorpholine (NMOR), N-nitrosopyrrolidine (NPYR), and N-nitrosodi-n-butylamine (NDBA) were detected in groundwater, with NDMA being the main compound detected (up to 52 ng L-1). Comparable concentrations of these N-nitrosamines were also found in river water. From laboratory experiments, we found a tremendous potential for the formation of N-nitrosamines in groundwater. Principal component analysis and multiple linear regression analysis results showed that the primary sources of N-nitrosamines in groundwater were the uses of nitrogen fertilizers and pesticides carrying specific N-nitrosamines such as NPYR. The average total carcinogenic risk values of detected N-nitrosamines were higher than the acceptable risk level (10-5), suggesting a potential carcinogenic risk of groundwater. Further research is urgently needed to minimize N-nitrosamine levels in the groundwater of agricultural areas, particularly in those where pesticides and fertilizers are heavily used.

Occurrence and transport of N-nitrosamines in the urban water systems of the Pearl River Delta, southern China.

The discharge of substantial amounts of N-nitrosamines-contained wastewater into receiving rivers can significantly deteriorate water quality, as these carcinogenic compounds can be easily transported into groundwater and drinking water systems. This study investigated the distribution of eight species of N-nitrosamines in river water, groundwater, and tap water located in the center of the Pearl River Delta (PRD), China. The results showed that three major N-nitrosamines, including N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), and N-nitrosodibutylamine (NDBA), with concentrations of up to 64 ng/L, were observed in river water, groundwater, and tap water, whereas the other compounds occurred sporadically. In river water and groundwater, high concentrations of NDMA, NDEA, N-nitrosomorpholine (NMOR), and NDBA were found in industrial and residential lands as compared to agricultural lands owing to the influence of various human activities. The primary sources of N-nitrosamines in river water were industrial and domestic wastewater, and the infiltration of river water was responsible for the high levels of N-nitrosamines in groundwater. Among the target N-nitrosamines, NDEA and NMOR with long biodegradation half-lives (>4 days) and low LogKow values (<1) displayed the highest potential for groundwater. N-nitrosamines in groundwater and tap water pose significant potential cancer risks to residents, especially children, and juveniles, with lifetime cancer risks of over 10-4, necessitating advanced water treatments for drinking water and critical controls on primary industrial discharge in urban areas.

Occurrence and mass loads of N-nitrosamines discharged from different anthropogenic activities in Desheng River, South China.

N-nitrosamines are widespread in various bodies of water, which is of great concern due to their carcinogenic risks and harmful mutagenic effects. Livestock rearing, domestic, agricultural, and industrial wastewaters are the main sources of N-nitrosamines in environmental water. However, information on the amount of N-nitrosamines these different wastewaters contribute to environmental water is scarce. Here, we investigated eight N-nitrosamines and assessed their mass loadings in the Desheng River to quantify the contributions discharged from different anthropogenic activities. N-nitrosodimethylamine (NDMA) (< 1.6-18 ng/L), N-nitrosomethylethylamine (NMEA) (< 2.2 ng/L), N-nitrosodiethylamine (NDEA) (< 1.7-2.4 ng/L), N-nitrosopyrrolidine (NPYR) (< 1.8-18 ng/L), N-nitrosomorpholine (NMOR) (< 2.0-3.5 ng/L), N-nitrosopiperidine (NPIP) (< 2.2-2.5 ng/L), and N-nitrosodi-n-butylamine (NDBA) (< 3.3-16 ng/L) were detected. NDMA and NDBA were the dominant compounds contributing 89% and 92% to the total N-nitrosamine concentrations. The mean cumulative concentrations of N-nitrosamines in the livestock rearing area (26 ± 11 ng/L) and industrial area (24 ± 4.8 ng/L) were higher than those in the residential area (16 ± 6.3 ng/L) and farmland area (15 ± 5.1 ng/L). The mean concentration of N-nitrosamines in the tributaries (22 ng/L) was slightly higher than that in the mainstem (17 ng/L), probably due to the dilution effect of the mainstem. However, the mass loading assessment based on the river's flow and water concentrations suggested the negligible mass emission of N-nitrosamines into the mainstem from tributaries, which could be due to the small water flow of tributaries. The average mass loads of N-nitrosamines discharged into the mainstem were ranked as the livestock rearing area (742.7 g/d), industrial area (558.6 g/d), farmland area (93.9 g/d), and residential areas (83.2 g/d). In the livestock rearing, residential, and industrial area, NDMA (60.9%, 53.6%, and 46.7%) and NDBA (34.6%, 33.3%, and 44.9%) contributed the most mass loads; NDMA (23.4%), NDEA (15.8%), NPYR (10.1%), NPIP (12.8%), and NDBA (37.8%) contributed almost all the mass loads in the farmland area. Photodegradation amounts of NDMA (0.65 ~ 5.25 µg/(m3·day)), NDBA (0.37 ~ 0.91 µg/(m3·day)), and NDEA (0 ~ 0.66 µg/(m3·day)) were also calculated according to the mass loading. Quantifying the contribution of different anthropogenic activities to the river will provide important information for regional river water quality protection. Risk quotient (RQ) values showed the negligible ecological risks for fish, daphnid, and green algae.

Integration of Zeolite Membrane Bioreactor With Granular Sludge-Based Anammox in High-Efficiency Nitrogen Removal From Iron Oxide Red Wastewater.

Acquisition of stable nitritation and efficient anammox play a crucial role in partial nitritation (PN) combined with anammox for nitrogen removal from ammonium-rich wastewater. Due to the limitation of ammonia-oxidizing bacteria (AOB) enrichment and nitrite-oxidizing bacteria (NOB) control in traditional membrane biological reactor (MBR), it can result in a lower nitrite production rate (NPR) and unstable PN, eventually reducing the nitrogen removal rate (NRR) via PN-anammox. In this study, we developed a zeolite membrane biological reactor (ZMBR) to enhance the PN of iron oxide red wastewater (IORW), in which the biofilm derived from the zeolite surface can provide free ammonia (FA)-containing microenvironment for AOB enrichment and NOB inhibition. The results showed that ZMBR can tolerate a higher influent nitrogen loading rate (NLR) of 2.78 kg/(m3⋅day) in comparison to the traditional MBR [2.02 kg/(m3⋅day)] and the NPR in ZMBR and traditional MBR were 1.39 and 0.96 kg/(m3⋅day), respectively. The mass concentration ratio of NO 2 - -N/ NH 4 + -N ranged from 1.05 to 1.33 in ZMBR, suggesting a suitable condition for nitrogen removal via anammox. Subsequently, the domesticated granular sludge obtained from a paper-making wastewater treatment was used as the carrier of anammox bacteria to remove nitrogen. After 93 days of operation, the NRR was observed to be 2.33 kg/(m3⋅day) and high-throughput sequencing indicated that the relatively higher abundance (45.0%) of Candidatus Kuenenia stuttgartiensis was detected in the granular sludge of the bottom part of the reactor, which can produce more proteins and lipids, suggesting a good settleability. Overall, this study provides a high-efficient method to control PN and domesticate anammox for nitrogen removal from IORW.

Characterization, dissolution and solubility of synthetic cadmium hydroxylapatite [Cd5(PO4)3OH] at 25-45°C.

BACKGROUND: The substitution of Ca(2+) in Ca-hydroxylapatite by toxic Cd(2+) can cause the forming of Cd-hydroxylapatite and is a significant issue in a great variety of research areas, which hence needs an understanding of the essential physicochemical characteristics. Unfortunately, the solubility product and thermodynamic data for Cd-hydroxylapatite in water under a variety of conditions now are lacking. Little information has been reported by previous researchers. Additionally, the dissolution mechanism of Cd-hydroxylapatite has never been studied. RESULTS: Dissolution of the synthetic cadmium hydroxylapatite [Cd-HAP, Cd5(PO4)3OH] in HNO3 solution (pH = 2), ultrapure water (pH = 5.6) and NaOH solution (pH = 9) was experimentally studied at 25, 35 and 45°C. Characterization by XRD, FT-IR and FE-SEM proved that Cd-HAP solids showed no recognizable change during dissolution. For the Cd-HAP dissolution in aqueous acidic media at initial pH 2 and 25°C, the solution cadmium and phosphate concentrations increased rapidly and reached the peak values after 20-30 days and 10 days reaction, respectively. Thereafter, the Cd-HAP dissolution rate decreased slowly, whereas the solution Cd/P molar ratio increased constantly from 1.65-1.69 to 6.61-6.76. The mean K sp values for Cd5(PO4)3OH were determined to be 10(-64.62) (10(-64.53)-10(-64.71)) at 25°C, 10(-65.58) (10(-65.31)-10(-65.80)) at 35°C and 10(-66.57) (10(-66.24)-10(-66.90)) at 45°C. Based on the obtained solubility data from the dissolution at initial pH 2 and 25°C, the Gibbs free energy of Cd5(PO4)3OH forming [Formula: see text] was determined to be -3,970.47 kJ/mol (-3,969.92 to -3,970.96 kJ/mol). Thermodynamic parameters, ΔG (0), ΔH (0), ΔS (0), and [Formula: see text] for the dissolution process of Cd-HAP in aqueous acidic media at initial pH 2 and 25°C were calculated 368,710.12 J/K mol, -158,809.54 J/mol, -1,770.20 and -869.53 J/K mol, respectively. CONCLUSIONS: Based on the experimental results of the present work and some previous researches, the cadmium hydroxylapatite (Cd-HAP) dissolution in aqueous media is considered to have the following coincident processes: the stoichiometric dissolution coupled with protonation and complexation reactions, the non-stoichiometric dissolution with Cd(2+) release and PO4 (3-) sorption and the sorption of Cd(2+) and PO4 (3-) species from solution backwards onto Cd-HAP surface. The obtained solubility products (K sp) 10(-64.62) (10(-64.53)-10(-64.71)) for Cd-HAP was approximately 7.62-5.62 log units lower than 10(-57)-10(-59) for calcium hydroxylapatite (Ca-HAP).Graphical abstractDissolution of cadmium hydroxylapatite [Cd5(PO4)3OH].