With the extensive application of graphene oxide (GO), it is noticeable that part of GO is directly/indirectly released into the environment and widespread research indicated that it had adverse influences on human health and ecological balance. In this work, a novel nanobelt-like Ca/Al layered double hydroxides (CA-LDH) was synthesized and applied as efficient coagulant for the removal of GO from aqueous solutions. The results indicated that neutral pH, co-existing cations and higher temperature were beneficial to the coagulation of GO. The sequence of cation effect for promoting of GO coagulation was Ca2+ > Mg2+ > K+ > Na+, whereas the effect of anions on GO coagulation was PO43− > CO32− > SO42− > Cl−. Comparing with anions, the cations showed more dominate effect for GO coagulation than anions. Hydrogen bonds and electrostatic interaction were the main coagulation mechanisms for GO coagulation, which were evidenced by FT-IR and XPS analysis. Specifically, for the first time, the reclaimed product of CA-LDH after GO coagulation (CA-LDH + GO) was applied as adsorbents for the secondary application in the removal of heavy metal ions from aqueous solutions. Interestingly, the CA-LDH + GO still had high adsorption capacities, i.e., the maximum adsorption capacities (qmax) for Cu(II), Pb(II), and Cr(VI) were 122.7 mg/g, 221.2 mg/g and 64.4 mg/g, respectively, higher than other similar materials. This paper highlighted the LDH-based nanomaterials are promising materials for the elimination of environmental pollutants and the migration and transformation of carbon nanomaterials in the natural environment.

Human external exposure (i.e. intake) of organophosphate flame retardants (PFRs) has recently been quantified, but no link has yet been established between external and internal exposure. In this study, we used a pharmacokinetic (PK) model to probe the relationship between external and internal exposure data for three PFRs (EHDPHP, TNBP and TPHP) available for a Norwegian cohort of 61 individuals from 61 different households. Using current literature on metabolism of PFRs, we predicted the metabolite serum/urine concentrations and compared it to measured data from the study population. Unavailable parameters were estimated using a model fitting approach (least squares method) after assigning reasonable constraints on the ranges of fitted parameters. Results showed an acceptable comparison between PK model estimates and measurements (<10-fold deviation) for EHDPHP. However, a deviation of 10–1000 was observed between PK model estimates and measurements for TNBP and TPHP. Sensitivity and uncertainty analysis on the PK model revealed that EHDPHP results showed higher uncertainty than TNBP or TPHP. However, there are indications that (1) current biomarkers of exposure (i.e. assumed metabolites) for TNBP and TPHP chemicals might not be specific and ultimately affecting the outcome of the modeling and (2) some exposure pathways might be missing. Further research, such as in vivo laboratory metabolism experiments of PFRs including identification of better biomarkers will reduce uncertainties in human exposure assessment.

The present study aimed to investigate biodegradation mechanisms of black carbon (BC)-bound contaminants in BC-amended sediment when BC was applied to control organic pollution. The single-point Tenax desorption technique was applied to track the species changes of nonylphenol (NP) during biodegradation process in the rice straw carbon (RC)-amended sediment. And the correlation between the biodegradation and desorption of NP was analyzed. Results showed that microorganisms firstly degraded the rapid-desorbing NP (6 h Tenax desorption) in RC-amended sediment. The biodegradation facilitated the desorption of slow-desorbing NP, which was subsequently degraded as well (192 h Tenax desorption). Notably, the final amount of NP degradation was greater than that of NP desorption, indicating that absorbed NP by RC amendment can be degraded by microorganisms. Finally, the residual NP amount in RC-amended sediment was decided by RC content and its physicochemical property. Moreover, the presence of the biofilm was observed by the confocal laser scanning microscope (CLSM) and scanning electron microscope (SEM) so that microorganisms were able to overcome the mass transfer resistance and directly utilized the absorbed NP. Therefore, single-point Tenax desorption alone may not be an adequate basis for the prediction of the bioaccessibility of contaminants to microorganisms or bioremediation potential in BC-amended sediment.

The broad application of triclosan (TCS) and triclocarban (TCC) as antimicrobials in household and personal care products has led to the concerns regarding their human health risk and environmental impact. Although many studies have examined the toxicological effects of these compounds to a wide range of aquatic organisms from algae to fish, their potential toxicity to an important model organism the nematode Caenorhabditis elegans has never been systematically investigated. Here we assessed the toxicological effects of TCS and TCC in C. elegans using endpoints from organismal to molecular levels, including lethality, reproduction, lifespan, hatching, germline toxicity, and oxidative stress. L4 stage or young adult worms were exposed to TCS or TCC and examined using above-mentioned endpoints. Both TCS and TCC showed acute toxicity to C. elegans, with 24-h LC50s of 3.65 (95% CI: 3.15, 4.3) mg/L and 0.91 (95% CI: 0.47, 1.53) mg/L, respectively. TCS at 0.1–2 mg/L and TCC at 0.01–0.5 mg/L, respectively, induced concentration dependent reduction in the worm's reproduction, lifespan, and delay in hatching. Using a DAF-16:GFP transgenic strain, we found both compounds induced oxidative stress in the worm, indicated by the relocalization of DAF-16:GFP from cytoplasm to the nucleus upon exposure. Germline toxicity of the two compounds was also demonstrated using a xol-1:GFP transgenic strain. These findings suggest that TCS and TCC induce systemic toxic effects in C. elegans. Further studies are needed to elucidate the potential mechanisms of toxicity of these antimicrobials in the model organism, especially their potential endocrine disruption effects.

A total of 82 aerosol samples (PM10-2.5) were collected from June 18, 2015 to October 1, 2016 at the remote sea site, the Ieodo Ocean Research Station (IORS), in the East China Sea. Samples were analyzed for 10 elements (Al, Fe, Cu, Zn, As, Mo, Cd, Sb, Tl, and Pb) as well as Pb isotopic composition to characterize temporal variations in elemental concentration levels, and to identify the potential source regions of atmospheric pollutants transported over the remote East China Sea. The results showed that the annual average element concentrations were lowest compared to those at different sites in East Asia, suggesting a very clean background area of IORS, with values ranging from 114 ng m⁻³ for Al to 0.045 ng m⁻³ for Tl. Concentrations averaged seasonally for all the elements revealed the highest levels occurring between winter and spring, and the lowest levels in summer. High enrichment factors (EF) of more than 100 for trace elements suggest that these elements originated mostly from anthropogenic sources. Coupling the Pb isotopic composition with a back trajectory analysis identified the potential source regions for each sample. Our approach identified China as a dominant contributor affecting atmospheric composition changes at IORS, the remote area of the East China Sea. As the largest anthropogenic emission source in East Asia, China contributed to almost 100% of the elemental concentration levels in winter and spring, ∼53% in summer and ∼63% in autumn. Because IORS's ambient air is sensitive to even slight changes in pollutant loading due to the significantly low pollution levels, long-term monitoring of air quality at IORS will provide invaluable information on the progress and efforts of atmospheric pollution management linked to emission controls in East Asian countries, especially China.

Mining activities have contaminated many riverine floodplains with arsenic (As). When floodplain soils become anoxic under water-saturated conditions, As can be released from the solid phase. Several microbially-driven As solubilization processes and numerous influential factors were recognized in the past. However, the interplay and relative importance of soil properties and the influence of environmental factors such as temperature remain poorly understood, especially considering the (co)variation of soil properties in a floodplain. We conducted anoxic microcosm experiments at 10, 17.5, and 25 °C using 65 representative soils from the mining-impacted Ogosta River floodplain in Bulgaria. To investigate the processes of As solubilization and its quantitative variation we followed the As and Fe redox dynamics in the solid and the dissolved phase and monitored a range of other solution parameters including pH, Eh, dissolved organic C, and dissolved Mn. We related soil properties to dissolved As observed after 20 days of microcosm incubation to identify key soil properties for As solubilization. Our results evidenced reductive dissolution of As-bearing Fe(III)-oxyhydroxides as the main cause for high solubilization. The availability of nutrients, most likely organic C as the source of energy for microorganisms, was found to limit this process. Following the vertical nutrient gradient common in vegetated soil, we observed several hundred μM dissolved As after 1–2 weeks for some topsoils (0–20 cm), while for subsoils (20–40 cm) with comparable total As levels only minor solubilization was observed. While high Mn contents were found to inhibit As solubilization, the opposite applied for higher temperature (Q10 2.3–6.1 for range 10–25 °C). Our results suggest that flooding of nutrient-rich surface layers might be more problematic than water-saturation of nutrient-poor subsoil layers, especially in summer floodings when soil temperature is higher than in winter or spring.

Microcystin-LR (MCLR) has been reported to cause developmental neurotoxicity in zebrafish, but there are few studies on the mechanisms of MCLR-induced transgenerational effects of developmental neurotoxicity. In this study, zebrafish were exposed to 0, 1, 5, and 25 μg/L MCLR for 60 days. The F1 zebrafish embryos from the above-mentioned parents were collected and incubated in clean water for 120 h for hatching. After examining the parental zebrafish and F1 embryos, MCLR was detected in the gonad of adults and F1 embryos, indicating MCLR could potentially be transferred from parents to offspring. The larvae also showed a serious hypoactivity. The contents of dopamine, dihydroxyphenylacetic acid (DOPAC), serotonin, gamma-aminobutyric acid (GABA) and acetylcholine (ACh) were further detected, but only the first three neurotransmitters showed significant reduction in the 5 and 25 μg/L MCLR parental exposure groups. In addition, the acetylcholinesterase (AChE) activity was remarkably decreased in MCLR parental exposure groups, while the expression levels of manf, bdnf, ache, htr1ab, htr1b, htr2a, htr1aa, htr5a, DAT, TH1 and TH2 genes coincided with the decreased content of neurotransmitters (dopamine, DOPAC and serotonin) and the activity of AChE. Neuronal development related genes, α1-tubulin, syn2a, mbp, gfap, elavl3, shha and gap43 were also measured, but gap43 was the gene only up-regulated. Our results demonstrated MCLR could be transferred to offspring, and subsequently induce developmental neurotoxicity in F1 zebrafish larvae by disturbing the neurotransmitter systems and neuronal development.

Cadmium uptake in rice is believed to be mediated by the Fe transport system. Phyto-available Cd can be changed by Fe fertilization of substrates. This work investigated whether and how Fe fertilization affects mitigation of Cd accumulation in paddy rice. A 90-d soil column experiment was conducted to study the change of Cd and Fe availability in soil after Fe fertilization (ionic and chelated Fe). A low-Cd accumulating cultivar (TY116) and a high-Cd accumulating cultivar (JY841) were grown in two Cd-polluted paddy soils amended with chelated Fe fertilizers. Additionally, both cultivars were grown in hydroponics to compare Fe-related gene expression in EDDHAFe-deficient and EDDHAFe-sufficient roots.The column experiment showed that EDTANa2Fe(II) and EDDHAFe(III) fertilization had a better mitigation effect on soil Cd availability compared to FeSO4·7H2O. Moreover, the field experiment demonstrated that these two chelated fertilizations could reduce Cd concentrations in brown rice by up to 80%. Iron concentrations in the brown rice were elevated by Fe chelates. Compared to EDDHAFe(III), EDTANa2Fe(II) fertilization had a stronger mitigation effect by generating more EDTANa2Cd(II) in the soil solution to decrease phyto-available Cd in the soil. While EDDHAFe(III) fertilization could increase soil pH and decrease soil Eh which contributed to decreasing phyto-available Cd in a contaminated soil. In the hydroponic experiment, Fe sufficiency significantly reduced Cd concentrations in above-ground organs. In some cases, the expression of OsIRT1, OsNRAMP1 and OsNRAMP5 was inhibited under Fe sufficiency relative to Fe deficiency conditions. These results suggest that mitigation of rice Cd by Fe chelate fertilization results from a decrease in available Cd in substrates and the inhibition of the expression of several Fe-related genes in the IRT and NRAMP families.

Perturbations of rainwater chromophoric dissolved organic matter (CDOM) fluorescence induced by changes in rainfall intensity and pH were investigated by field observations and laboratory pH titrations. Microbial humic-like fluorophores dominated the rainwater CDOM pool, followed by tryptophan-like and tyrosine-like substances. Increased rainfall intensity had notable dilution effects on all six fluorescent components (C1-C6) identified using parallel factor (PARAFAC) analysis, the effect being especially pronounced for the microbial humic-like C1, tryptophan-like C3, and tyrosine-like C5. The results also indicated that increasing pH from 7 to 9 led to decreased fluorescence intensity (Fmax) of all the six components, while a pH increase from 5 to 7, resulted in increasing Fmax of terrestrial humic-like C2, tyrosine-like C5, and tryptophan-like C6 and decreasing microbial humic-like C1, tryptophan-like C3, and fulvic-like C4. Two-dimensional correlation spectroscopy (2D-COS) demonstrated that synchronous fluorescence responded first to pH modifications at fulvic-like wavelength (λEx/λEm = ∼316/416 nm), followed by tyrosine-like wavelength (λEx/λEm = ∼204/304 nm), tryptophan-like wavelength (λEx/λEm = ∼226/326 nm), microbial humic-like wavelength (∼295/395 nm), and finally terrestrial humic-like wavelength (∼360/460 nm). Our results suggest that a decrease in areas affected by acid rain in South China occurring at present may possibly result in apparent compositional changes of CDOM fluorescence. The decreased rainfall in South-West China and increased rainfall in North-West China during the past five decades may possibly accordingly result in increased and decreased Fmax of all the six components identified in South-West and North-West China, respectively.

Phosphorus (P) plays a critical role in algal growth; therefore, a better understanding of P availability is essential to control harmful algal blooms. Three algae species, Microcystis aeruginosa, Chlorella pyrenoidosa, and Pseudokirchneriella subcapitata, were mono-cultured and co-cultured on three types of P substrates, dissolved inorganic P (DIP), phosphomonoesters glucose-6-phosphate (G-6-P) and β-glycerol phosphate (β-glycerol-P), and phosphonate (glyphosate), to explore their growth and P utilization. All three species could utilize dissolved organic P (DOP) to sustain their growth, whereas DIP was their preferred P substrate in both culture types. Algae could regulate the P uptake capacity under different P conditions, and the added P could be rapidly accumulated at the beginning of the culture and slowly utilized during the subsequent life cycle. M. aeruginosa exhibited wider P selectivity and could utilize all three P substrates, whereas the other two species could only use phosphomonoester (G-6-P and β-glycerol-P) in the mono-cultures. However, in the co-cultures, the relative bioavailability of DOP for M. aeruginosa and C. pyrenoidosa was enhanced, and M. aeruginosa might contribute to the growth of C. pyrenoidosa and P. subcapitata when fed with glyphosate. The three species showed an intrinsic ability to produce alkaline phosphatase (AP), and AP activity (APA) was regulated by Pi stress. However, high APA did not necessarily lead to high Pi release and algal growth on unfavorable substrates. Although M. aeruginosa was not superior in growth rate in the mono-cultures, it showed a better P accumulation ability and maintained stable growth on different P substrates. Moreover, it was a good competitor, suppressing the thriving growth of the other species in co-cultures. Overall, the findings indicated the strategic flexibility of P utilization by algae and the strong competitive ability of M. aeruginosa in Pi-limited and DOP-enriched natural waters.