A microcosm evaluation of metal cycling in an urbanized contaminated estuary varying with oxic-hypoxic-anoxic-reoxic transition: Behavior, fluxes, and mechanism.

Water hypoxia and metal pollution are commonly co-existed in urbanized estuaries. This study focuses on the effect of an extended dissolved oxygen (DO) full-life dynamics (86 days) on metal behavior across the sediment-water interface through laboratory microcosms from two typical zones in Pearl River Estuary. Combining our time-series results of concentrations and fluxes, it showed that Co, Ni, and Zn consistently presented a release-precipitation-release trajectory with an oxic-hypoxic-anoxic-reoxic transition, characterized with highly variable behavior in the hypoxic-anoxic hotmoments. In parallel, changing DO dynamics significantly activated a repartitioning process of Co, Ni, and Zn among several species and elevated their risk in sediments, promoting the formation of more labile species in the 0-10 mm hotspots, where metals sensitively responded. Over DO transition, metal cycling was tightly co-related with Fe, Mn, and S elements. It was found that Mn was dominated in low oxygen-hypoxic period, but switched to S and Fe in anoxic stage, limiting sustained metal liberation to overlying water. Enlarging this experiment to practice, released Zn fluxes from sediments in hypoxic summer could contribute about ∼2.0% to their stocks in water column, while increase to 20% (1 m bottom water) in highly-stratified zones. This study has certain significance in understanding the long-term metal behavior and fate in estuarine regions, even lakes and reservoirs.

A review of the formation conditions and assessment methods of black and odorous water.

Black and odorous water is an extreme pollution phenomenon. This article reviews the formation process, formation conditions, and evaluation methods of black and odorous water. The results indicate that N, P, and TOC are the key nutrients inducing black and odorous water while S, Fe, and Mn are key elements forming blackening and odorizing pollutants. In addition, Cyanobacteria, Proteobacteria, Firmicutes, Verrucomicrobia, Planctomycetes, and Actinobacteria participate in the biogeochemistry cycles of key elements and play important roles in the blackening and odorizing process of water. The black and odorous thresholds that need further verification are as follows: 1.0 g/L of organic matrix, 2.0-8.0 mg/L of NH3-N, 0.6-1.2 mg/L of TP, 0.05 mg/L of Fe2+, 0.3 mg/L of Mn2+, 1.2-2.0 mg/L of DO, and -50 to 50 mV of the ORP. In order to propose a universal assessment method, it is suggested that NH3-N, DO, COD, BOD, and TP serve as the assessment indicators, and the levels of pollutions are I (not black odor), II (mild black odor), III (moderate black odor), IV (severe black odor), and inferior IV (extremely black odor).

Assessment of heavy metals remobilization and release risks at the sediment-water interface in estuarine environment.

The influence of overlying hydrodynamics on the exchange behaviour and fluxes of heavy metals at the sediment-water interface (SWI) is poorly understood. In the study, metals exchange behaviour and exchange rate at the SWI under resuspended and undisturbed scenario were investigated The results showed that dissolved Cr, Cu, Zn, and Pb concentrations increased rapidly to attain maximum values between 0.3 and 0.5 N·m-2 after the sediment resuspended. Following the quick release, metals concentrations gradually decreased and remained at relatively low levels, especially for Cu and Zn. Meanwhile, Cu, Zn, and Pb had higher potential remobilization potential in the undisturbed case. Calculating with the hydrodynamics in the Modaomen, the metals efflux under the resuspension scenario could reach 0.55 to 4130.83 mg·m-2·yr-1, which were 1-3 orders of magnitudes higher than the undisturbed case. Whether or not resuspension events occurred, estuarine sediments were source of heavy metals, especially in the weakly mixed zone.

Two Ratiometric Fluorescent Probes Based on the Hydroxyl Coumarin Chalcone Unit with Large Fluorescent Peak Shift for the Detection of Hydrazine in Living Cells.

Hydrazine is widely used in industrial and agricultural production, but excessive hydrazine possesses a serious threat to human health and environment. Here two new ratiometric fluorescence probes, DDP and DDC, with the hydroxyl coumarin chalcone unit as the sensing site are developed, which can achieve colorimetric and ratiometric recognition for hydrazine with good sensitivity, excellent selectivity, and anti-interference. The calculated fluorescence limits of detections are 0.26 µM (DDC) and 0.14 µM (DDP). The ratiometric fluorescence response to hydrazine is realized through the adjustment of donor and receptor units in coumarin conjugate structure terminals, accompanied by fluorescence peak shift about 200 nm (DDC, 188 nm; DDP, 229 nm). Stronger electropositivity in the carbon-carbon double bond is helpful to the first phase addition reaction between the probe and hydrazine. Higher phenol activity in the hydroxyl coumarin moiety will facilitate the following dihydro-pyrazole cyclization reaction. In addition, both of these probes realized the convenient detection of hydrazine vapor. The probes were also successfully applied to detect hydrazine in actual water samples, different soils, and living cells.

A julolidine-chalcone-based fluorescent probe for detection of Al3+ in real water sample and cell imaging.

A fluorescent probe 1 based on julolidine-chalcone derivative, which can specifically recognize aluminum ion with high selectivity and anti-interference, was developed. Probe 1 has good fluorescence stability and can detect Al3+ with turn-on fluorescence in a wide pH range of 4.0-9.0. The probe has good repeatability for the detection of Al3+ and fluorescence turn-on and off can be repeated with the alternate Al3+ and EDTA. The sensing mechanism is speculated that Al3+ will coordinate with hydroxyl oxygen and carbonyl oxygen on the probe through in situ 1H NMR and HRMS combing with Job's plot. The probe can also detect Al3+ in actual water samples and applied to monitor Al3+ in biological system.

Distribution and partitioning of heavy metals in water and sediments of a typical estuary (Modaomen, South China): The effect of water density stratification associated with salinity.

Many estuaries have undergone severe saltwater intrusion in addition to simultaneously experiencing serious heavy metal pollution. To explore the effect of water density stratification associated with saltwater intrusion on the behaviour of heavy metals (Cr, Co, Ni, Cu, Zn, As, Pb, and Cd) in water and sediments, a field survey was conducted in a typical estuary (Modaomen). The content, distribution, and mobility of heavy metals were investigated, as well as the influence of environmental factors on their future. The results showed that Modaomen estuary was characterised by a notable variation in salinity along the estuary, presenting total freshwater upstream, high salinity stratification water in the mouth, and saltwater offshore. Dissolved metals presented a prominent gradient vertically, with 1.2-2.1 times higher in bottom water than in surface water and the highest contents in the highly-stratified bottom water. Elevated salinity and restricted mixing induced by water stratification were likely the causes of this outcome. The distribution of heavy metals in sediments was greatly governed by grain size, Fe/Mn (hydr)oxides, total organic carbon, salinity, and dissolved oxygen. Comprehensive evaluation, combined with total contents and chemical fractions of heavy metals, indicated that internal release from sediments contributed a considerable part to the higher levels of heavy metals in bottom water, particularly for Zn and Pb, which was fully consistent with their status in water body, and elevated salinity and lack of oxygen were likely the primary driving factors. During the phase-partition processes between bottom water and sediments, partitioning coefficients were markedly lower in the highly stratified zone, implying that saltwater intrusion facilitated the mobility and repartitioning processes of metals. Because of increased levels and toxicity of heavy metals in water and extended residence time during saltwater intrusion, the potential damage to the estuarine ecosystem should receive more attention.

Assessment of heavy metal pollution, distribution and quantitative source apportionment in surface sediments along a partially mixed estuary (Modaomen, China).

The aim of this study is to investigate the distribution, ecological risk and quantitative source apportionment of seven heavy metals in surface sediments along a partially mixed estuary (Modaomen, China). The study area was divided into three regions based on salt-freshwater mixing: a tidal river channel, weakly mixed zone and strongly mixed zone. The concentrations of Cu, Zn, Pb, Cd, Cr and Ni were significantly higher in the weakly mixed zone, while a higher Co content was found in the tidal river channel. From enrichment factor (EF) analyses, Cd was moderate to extreme severely enriched at most stations, and other heavy metals were minor enrichments. Adverse effects on aquatic biota may occur occasionally for all seven heavy metals based on the sediment quality guidelines (SQGs). The correlations between Al and heavy metals suggested that metals in sediments were mainly attributed to anthropogenic sources. Then Positive matrix factorization (PMF) and Geostatistic method were used to quantify the heavy metal sources and determine impacted regions. A mixed source from the inner Lingding Bay and West River contributed approximately 50% of the Cu, Zn, Pb, Cr and Ni. The electroplating industry accounted for about 57% of the Cd content, and the major contaminated area was concentrated at the confluence of the West River and its tributaries. The alloy industry contributed approximately 65% of the Co, most of which was near an industrial park.

A combined process coupling phytoremediation and in situ flushing for removal of arsenic in contaminated soil.

Phytoremediation and soil washing are both potentially useful for remediating arsenic (As)-contaminated soils. We evaluated the effectiveness of a combined process coupling phytoremediation and in situ soil flushing for removal of As in contaminated soil through a pilot study. The results showed that growing Pteris vittata L. (P.v.) accompanied by soil flushing of phosphate (P.v./Flushing treatment) could significantly decrease the total As concentration of soil over a 37day flushing period compared with the single flushing (Flushing treatment). The P.v./Flushing treatment removed 54.04% of soil As from contaminated soil compared to 47.16% in Flushing treatment, suggesting that the growth of P. vittata was beneficial for promoting the removal efficiency. We analyzed the As fractionation in soil and As concentration in soil solution to reveal the mechanism behind this combined process. Results showed that comparing with the control treatment, the percent of labile arsenate fraction significantly increased by 17% under P.v./Flushing treatment. As concentration in soil solution remained a high lever during the middle and later periods (51.26-56.22mg/L), which was significantly higher than the Flushing treatment. Although soil flushing of phosphate for more than a month, P. vittata still had good accumulation and transfer capacity of As of the soil. The results of the research revealed that combination of phytoremediation and in situ soil flushing is available to remediate As-contaminated soils.

Planar Heptathienoacenes Based on Unsymmetric Dithieno[3,2-b:3',4'-d]thiophene: Synthesis and Photophysical Properties.

The unsymmetric dithieno[3,2-b:3',4'-d]thiophene (ts-DTT) was efficiently synthesized, and two novel heptathienoacenes with linear and bull's horn shapes were designed and prepared via different ring cyclization connection manners. All intermediates and aimed heptathienoacenes were fully characterized by (1)H NMR, (13)C NMR, and HRMS. Their UV-vis absorption behavior, fluorescence, and electrochemical properties are characterized. In addition, DFT quantum calculation was employed to further understand the electron distribution and the origin of the absorption bands.

[Effects of Soil Moisture on Phytoremediation of As-Containinated Soils Using As-Hyperaccumulator Pteris vittata L].

A pot experiment was carried out to study the effects of soil moisture on the growth and arsenic uptake of As-hyperaccumulator Pteris vittata L. The results showed that the remediation efficiency of As was the highest when the soil moisture was between 35%-45%. P. vittata grew best under 45% water content, and its aboveground and underground plant dry weights were 2.95 g x plant(-1) and 11.95 g x plant(-1), respectively; the arsenic concentration in aboveground and roots was the highest under 35% water content, and 40% content was the best for accumulation of arsenic in P. vittata. Moreover, controlling the soil moisture to 35%-45% enhanced the conversion of As(V) to As(III) in aboveground plant, and promoted arsenic detoxification in P. vittata. These above results showed that soil moisture played an important role in the absorption and transport of arsenic by P. vittata. The results of this study can provide important guidance for the large-scale planting of P. vittata and the moisture management measures in engineering application.

Characterization of PM(10) fraction of road dust for polycyclic aromatic hydrocarbons (PAHs) from Anshan, China.

Nineteen road dust samples were collected during 2005 in different parts of the urban area of Anshan, Liaoning Province, China, and 11 polycyclic aromatic hydrocarbons (PAHs) species were quantitatively analyzed using GC-MS. The results indicated that the total average concentration of PAHs over the investigated sites ranged from 48.73 to 638.26 microg/g, with a mean value of 144.25 microg/g, higher than the concentrations measured in previous studies. PAHs concentrations were higher with high molecular weight homologues (4-6 rings PAHs), accounting for 83.24-96.98%, showing combustion of petroleum fuels was a potential source. Organic carbon in road dust was considered one of the important factors that influenced the concentrations of PAHs in this study, and it was found that concentrations of total PAHs were correlated with those of organic carbon in road dust. The results of diagnostic ratios analysis showed traffic emission (gasoline or diesel) was one of the most important sources of road dust PAHs. Principal component analysis (PCA) indicated that the major sources of road dust PAHs might be emission from traffic, steel industry, cooking and coal combustion.