Novel use of ferrous iron/peroxymonosulfate for high-performance seawater desalination pretreatment under harmful algal blooms.

Marine harmful algae bloom (HAB) is a growing threat to desalination plants worldwide. This work proposes ferrous iron/peroxymonosulfate (Fe2+/PMS) as a novel pretreatment technology for seawater reverse osmosis (SWRO) under HAB. Herein, Fe2+/PMS achieved a significantly higher reduction of negative charge of algae-laden seawater as compared to conventional coagulation (i.e., coagulant is Fe3+), which thereby facilitated improved flocculation to remove algal cells, turbidity and algal organics matters (AOMs), and marine Ca2+ (∼430 mg/L) could partially contribute to the enhanced coagulation performance. A new understanding of the improved coagulation efficiency achieved with Fe2+/PMS in seawater has been proposed as compared to freshwater: seawater matrix (e.g., 504 mM Cl-) was demonstrated to significantly enhance the generation of high-valent iron (FeO2+) as the main reactive intermediate instead of the long-recognized Fe3+ and free radicals, as revealed by methyl phenyl sulfoxide (PMSO) probe, radicals scavenging analysis and electron spin resonance (ESR) spectra. This new mechanism is expected to provide valuable insights for the development of more novel oxidative seawater treatment technologies. Of note, while trade-off between particles and AOMs played an important role in membrane fouling reduction by different dosages of Fe2+/PMS, Fe2+/PMS with an optimal dosage of 0.1 mM/0.05 mM achieved an unprecedentedly higher reduction (95.26%) of modified fouling index (MFI) as compared to conventional coagulation (13.28%-42.36% with 0.1-0.2 mM of Fe3+). Optical-photothermal infrared spectromicroscopy with sub-micron spatial resolution was employed to analyze membrane foulants for the first time, and Fe2+/PMS was found to mainly cause reduced cake layer resistance, which was attributed to the collectively reduced concentration of algae cells, micro-particles with sizes from 2 to 10 µm, humic substances and biopolymers. Moreover, Fe2+/PMS resulted in lower dissolved Fe3+ (<0.027 mg/L) in ultrafiltration (UF) permeate, which would make it more reliable for SWRO operation as compared to conventional coagulation. When energy-intensive dissolved air flotation (DAF) was employed to withstand HAB, Fe2+/PMS outperformed it and was instrumental in achieving reduced MFI with 56.4% lower operational cost. In this context, Fe2+/PMS would facilitate a high-performance and low-cost pretreatment technology for seawater desalination plants under HAB.

Effects of manganese, iron and sulfur geochemistry on arsenic migration in the estuarine sediment of a small river in Xiamen, Southeast China.

The geochemistry of iron (Fe), manganese (Mn) and sulfur (S) and their effects on arsenic (As) mobility in the mudflats of small river estuaries remain unclear. Here, diffusive gradient in thin films (DGT) and high-resolution dialysis (HR-Peeper) techniques combined with a sequential extraction procedure (BCR) were employed to investigate As, Fe, Mn and S geochemistry in the mudflat of the Jiuxi River estuary, Southeast China. Grain size analysis indicated that fine-grained particles were likely to be deposited in the estuarine intertidal zone and coastal area. DGT and HR-Peeper results revealed that in the estuary and coastal area, the dissolved As in sediment in summer was controlled by Mn geochemistry, which includes not only the release of As through Mn/Fe reduction but also the stabilization of dissolved As in pore water. This stabilization of dissolved As may due to the formation of As-Mn-OM complexes. In winter, the significant positive correlations between DGT-Fe, DGT-Mn, DGT-As and DGT-S indicated that sulfate reduction was the start of As mobilization in sediment in winter. In both the estuary and the coastal area, the easily reducible Fe, Mn and As contents in intertidal sediment were higher than those in the subtidal zone. Combined with the As flux across the sediment-overlying water interface (SWI), these phenomena suggested that As in subtidal sediment diffused into overlying water and that As in overlying water tended to accumulate in the intertidal sediment. The total organic carbon content (TOC) and DGT results in the lower reach, estuary and coastal areas indicated that organic matter is the controlling factor of Fe/Mn reduction, sulfate reduction and As mobilization. The BCR test results showed higher reactive fraction contents of Fe, Mn and As in winter sediment, which threaten the overlying water quality.

Embryo Microinjection and Knockout Mutant Identification of CRISPR/Cas9 Genome-Edited Helicoverpa Armigera (Hübner).

The cotton bollworm, Helicoverpa armigera, is one of the most destructive pests in the world. A combination of molecular genetics, physiology, functional genomics, and behavioral studies has made H. armigera a model species in Lepidoptera Noctuidae. To study the in vivo functions of and interactions between different genes, clustered regularly interspaced short palindromic repeats (CRISPR)/ associated protein 9 (Cas9) genome editing technology is a convenient and effective method used for performing functional genomic studies. In this study, we provide a step-by-step systematic method to complete gene knockout in H. armigera using the CRISPR/Cas9 system. The design and synthesis of guide RNA (gRNA) are described in detail. Then, the subsequent steps consisting of gene-specific primer design for guide RNA (gRNA) creation, embryo collection, microinjection, insect rearing, and mutant detection are summarized. Finally, troubleshooting advice and notes are provided to improve the efficiency of gene editing. Our method will serve as a reference for the application of CRISPR/Cas9 genome editing in H. armigera as well as other Lepidopteran moths.

Kinetic characteristics of mobile Mo associated with Mn, Fe and S redox geochemistry in estuarine sediments.

Estuarine sediments are crucial repositories and incubators of molybdenum (Mo) during its transport from rivers to the ocean. Here, Mo mobility and related processes in estuarine sediments were explored using high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques. Better correlations were observed between dissolved Mn and Mo than between dissolved Fe and Mo, implying that Mn geochemistry plays a key role in dissolved Mo mobility via molybdate adsorption onto abundant Mn oxides and its substantial release upon intense Mn reduction. As a result, oxic intertidal sediments functioned as Mo sinks, and anoxic subtidal sediments functioned as Mo sources. The opposite vertical distributions between DGT-Labile S and DGT-Labile Mo indicated that the availability of labile Mo can be blocked by aqueous sulfide. However, the corresponding high concentrations of DGT-Labile S and dissolved Mo at subtidal sites demonstrated that the abundant dissolved Mo remobilized via Mn reduction was not effectively solidified by sulfide. Simulation with the DIFS model further verified that redox conditions and induced physicochemical processes are crucial factors controlling Mo mobility, with relatively low dissolved Mo concentrations but an adequate and steady resupply capacity of the bioavailable molybdate in intertidal sediments.

Remobilization and hypoxia-dependent migration of phosphorus at the coastal sediment-water interface.

Sediment internal phosphorus (P) loading can be tightly associated with overlying water hypoxia. However, the effects of long-term seasonal hypoxia on the geochemical transition of P in P-poor coastal sediment and how this transition is linked to the early diagenesis of iron (Fe), sulfur (S) and carbon are still poorly understood. Here, we conducted a one-year monthly field investigation to study the (im)mobilization and migration of P among coastal sediment, porewater and overlying water. The coherent distribution of soluble Fe and mobile P and decoupled distribution of labile S (soluble sulfide) and mobile P in the depth profiles indicate that the redox cycling of Fe (but not S) dominates P mobility. Nevertheless, the monthly variation in the porewater soluble reactive P (SRP) presented significant positive correlations with that of the overlying water SRP. This finding highlights that hypoxia-fueled SRP migration from overlying water rather than weak diagenetic P mobilization due to deficient organic matter and solid labile P is the crucial factor responsible for internal P mobility over long time scales. Although SRP tends to migrate from overlying water to porewater, the potential risk of sediment labile P remobilization and reliberation to the overlying water is considerable.

Distribution characteristics and release mechanisms of Pb in surface sediments in different aquatic environments.

As a trace heavy metal, lead (Pb) has many anthropogenic applications but also produces many environmental pollution problems because of its high toxicity. In this study, we combined two in situ high-resolution sampling techniques - high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) - with the DGT-induced fluxes in sediment (DIFS) model to explore the mechanism of Pb release and resupply between sediments and pore water in the lower reaches and estuary of the Jiuxi River and the adjacent coast. An analysis of the chemical forms of Pb in the sediments showed that the content of the acid-extractable fraction (F1) was higher at the coastal site than at the other sampling sites, which indicates that Pb in the coastal sediments had greater activity and was more likely to cause Pb pollution. The apparent diffusion fluxes of Pb across the sediment-water interface (SWI) in the lower reaches, estuary and coastal zone are negative, and the absolute value of Pb flux in the estuary is several times higher than that in the other two stations, indicating a strong downward Pb diffusion trend, which may be due to water pollution caused by the nearby sewage outlet. As an insensitive element to redox, Pb did not exhibit an obvious correlation with Fe. In particular, the high Pb concentration and strong downward diffusion trend of the overlying water in the estuary caused the significant negative correlation between Pb and Fe. The calculated results of the DIFS model show that the reduced layer in the intertidal zone along the coast has the highest R value, the highest desorption rate (k-1) and the shortest response time (Tc), indicating that sediment particles in the coastal intertidal zone supply Pb to the pore water at the fastest rate; consequently, Pb pollution in the coastal zone is worthy of further attention.

Cyclical patterns and (im)mobilization mechanisms of phosphorus in sediments from a small creek estuary: Evidence from in situ monthly sampling and indoor experiments.

Internal phosphorus (P) mobility is crucially important to overlying water ecosystems, while its spatiotemporal variations and mechanisms remain to be studied, especially in dynamic estuarine sediments. In this study, in situ monthly field sampling and indoor experiments were combined to measure the soluble reactive P (SRP), soluble Fe and diffusive gradients in thin films (DGT)-labile P/S in the overlying water, sediment and porewater in the Jiuxi River Estuary by employing high-resolution dialysis (HR-Peeper), the DGT technique and a MicroRhizon sampler. The consistent tendency between DGT-labile S and P in most seasons indicates that P mobilization was dominated by intense dissimilatory sulfate reduction (DSR), causing high SRP concentrations and active exchange with the overlying water. The circannual cyclical pattern of P is summarized, where in addition to temperature, monthly changes in runoff and tidal range are crucial external factors to control long-term P cycling via changed redox environments and terrigenous materials inputs. The mobile P, Fe and S present higher values during flood tides and lower values during ebb tides in tidal simulation experiments, demonstrating that the short-term cycling of P, Fe and S in intertidal surface sediments is highly redox-sensitive and controlled by tidal processes. The results also reveal that DSR greatly facilitates P mobility and release, while sediment oxidation and the induced enhancement in DIR and Fe cycling can effectively control P immobilization.

Metal/metalloid and phosphorus characteristics in porewater associated with manganese geochemistry: A case study in the Jiulong River Estuary, China.

Sediment porewater can be an important source of contaminants in the overlying water, but the mechanisms of metal(loid) and phosphorus (P) remobilization remain to be investigated. In this study, high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) samplers were used to determine the porewater dissolved iron (Fe), manganese (Mn), cobalt (Co), chromium (Cr), vanadium (V), selenium (Se), arsenic (As), P and DGT-Labile S in coastal sediments in the Jiulong River Estuary (JRE), China. The results showed that high concentrations of dissolved Mn, Se and P were present in the overlying water, indicating potential water pollution with excessive amounts of Mn, Se and P. The dissolved Mn concentrations in the porewater were higher than the dissolved Fe concentrations, especially at submerged sites, demonstrating that Mn(III/IV) reduction is the dominant diagenetic pathway for organic carbon (OC) degradation, which directly affects Fe cycling by the competitive inhibition of Fe(III) reduction and Fe(II) reoxidation. Dissolved Co, Cr, V, Se, As and P show significant positive correlations with Mn but nearly no correlations with Fe, suggesting that the mobility of these metal(loid)s and P is associated with Mn but not Fe cycling in this region. In addition, the coelevated concentrations of the metal(loid)s, P and Mn at the submerged sites are attributed to the strengthened Mn reduction coupled with OC degradation fueled by hypoxia. The higher positive diffusion fluxes of Mn, Se and P were consistent with the excess Mn, Se and P concentrations in the overlying water, together with the approximately positive fluxes of the other metal(loid)s, indicating that sediment Mn(III/IV) reduction and concomitant metal(loid) and P remobilization might be vital pathways for metal(loid) and P migration to the overlying water.