Effect of alginate on the aggregation kinetics of copper oxide nanoparticles (CuO NPs): bridging interaction and hetero-aggregation induced by Ca<Superscript>2+</Superscript>

The stability of CuO nanoparticles (NPs) is expected to play a key role in the environmental risk assessment of nanotoxicity in aquatic systems. In this study, the effect of alginate (model polysaccharides) on the stability of CuO NPs in various environmentally relevant ionic strength conditions was investigated by using time-resolved dynamic light scattering. Significant aggregation of CuO NPs was observed in the presence of both monovalent and divalent cations. The critical coagulation concentrations (CCC) were 54.5 and 2.9 mM for NaNO₃ and Ca(NO₃)₂, respectively. The presence of alginate slowed nano-CuO aggregation rates over the entire NaNO₃ concentration range due to the combined electrostatic and steric effect. High concentrations of Ca²⁺ (>6 mM) resulted in stronger adsorption of alginate onto CuO NPs; however, enhanced aggregation of CuO NPs occurred simultaneously under the same conditions. Spectroscopic analysis revealed that the bridging interaction of alginate with Ca²⁺ might be an important mechanism for the enhanced aggregation. Furthermore, significant coagulation of the alginate molecules was observed in solutions of high Ca²⁺ concentrations, indicating a hetero-aggregation mechanism between the alginate-covered CuO NPs and the unabsorbed alginate. These results suggested a different aggregation mechanism of NPs might co-exist in aqueous systems enriched with natural organic matter, which should be taken into consideration in future studies.

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Graphical abstract Hetero-aggregation mechanism of CuO nanoparticles and alginate under high concentration of Ca²⁺

     

Drought-tolerant <Emphasis Type="Italic">Streptomyces pactum</Emphasis> Act12 assist phytoremediation of cadmium-contaminated soil by <Emphasis Type="Italic">Amaranthus hypochondriacus</Emphasis>: great potential application in arid/semi-arid areas

Microbe-assisted phytoremediation provides an effective approach to clean up heavy metal-contaminated soils. However, severe drought may affect the function of microbes in arid/semi-arid areas. Streptomyces pactum Act12 is a drought-tolerant soil actinomycete strain isolated from an extreme environment on the Qinghai-Tibet Plateau, China. In this study, pot experiments were conducted to assess the effect of Act12 on Cd tolerance, uptake, and accumulation in amaranth (Amaranthus hypochondriacus) under water deficit. Inoculated plants had higher Cd concentrations (root 8.7–33.9 %; shoot 53.2–102.1 %) and uptake (root 19.9–95.3 %; shoot 110.6–170.1 %) than non-inoculated controls in Cd-treated soil. The translocation factor of Cd from roots to shoots was increased by 14.2–75 % in inoculated plants, while the bioconcentration factor of Cd in roots and shoots was increased by 10.2–64.4 and 53.9–114.8 %, respectively. Moreover, inoculation with Act12 increased plant height, root length, and shoot biomass of amaranth in Cd-treated soil compared to non-inoculated controls. Physiochemical analysis revealed that Act12 enhanced Cd tolerance in the plants by increasing glutathione, elevating superoxide dismutase and catalase activities, as well as reducing malondialdehyde content in the leaves. The drought-tolerant actinomycete strain Act12 can enhance the phytoremediation efficiency of amaranth for Cd-contaminated soils under water deficit, exhibiting potential for application in arid and semi-arid areas.     

Simultaneous determination of estrogenic odorant alkylphenols,chlorophenols, and their derivatives in water using online headspace solid phase microextraction coupled with gas chromatography-mass spectrometry

A simple online headspace solid-phase microextraction (HS-SPME) coupled with the gas chromatography-mass spectrometry (GC-MS) method was developed for simultaneous determination of trace amounts of nine estrogenic odorant alkylphenols and chlorophenols and their derivatives in water samples. The extraction conditions of HS-SPME were optimized including fiber selection, extraction temperature, extraction time, and salt concentration. Results showed that divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most appropriate one among the three selected commercial fibers, and the optimal extraction temperature, time, and salt concentration were 70 °C, 30 min, and 0.25 g/mL, respectively. The developed method was validated and showed good linearity (R ²?>?0.989), low limit of detection (LOD, 0.002–0.5 μg/L), and excellent recoveries (76–126 %) with low relative standard deviation (RSD, 0.7–12.9 %). The developed method was finally applied to two surface water samples and some of these target compounds were detected. All these detected compounds were below their odor thresholds, except for 2,4,6-TCAS and 2,4,6-TBAS wherein their concentrations were near their odor thresholds. However, in the two surface water samples, these detected compounds contributed to a certain amount of estrogenicity, which seemed to suggest that more attention should be paid to the issue of estrogenicity rather than to the odor problem.     

Increasing the recovery of heavy metal ions using two microbial fuel cells operating in parallel with no power output

The present study aimed to improve the performance of microbial fuel cells (MFCs) by using an intermittent connection period without power output. Connecting two MFCs in parallel improved the voltage output of both MFCs until the voltage stabilized. Electric energy was accumulated in two MFCs containing heavy metal ions copper, zinc, and cadmium as electron acceptors by connection in parallel for several hours. The system was then switched to discharge mode with single MFCs with a 1000-Ω resistor connected between anode and cathode. This method successfully achieved highly efficient removal of heavy metal ions. Even when the anolyte was run in sequencing batch mode, the insufficient voltage and power needed to recover heavy metals from the cathode of MFCs can be complemented by the developed method. The average removal ratio of heavy metal ions in sequencing batch mode was 67 % after 10 h. When the discharge time was 20 h, the removal ratios of zinc, copper, and cadmium were 91.5, 86.7, and 83.57 %, respectively; the average removal ratio of these ions after 20 h was only 52.1 % for the control group. Therefore, the average removal efficiency of heavy metal ions increased by 1.75 times using the electrons stored from the bacteria under the open-circuit conditions in parallel mode. Electrochemical impedance data showed that the anode had lower solution resistance and polarization resistance in the parallel stage than as a single MFC, and capacitance increased with the length of time in parallel.

     

Efficacy of Si fertilization to modulate the heavy metals absorption by barley (Hordeum vulgare L.) and pea (Pisum sativum L.)

Silicon-based fertilizers and soil amendments can have direct and indirect positive influences on cultivated plants. The solid forms of Si-based substances, the most widespread in use, are efficient only at high application rates due to their low level of solubility. Several types of Si-based substances such as fumed silica, slags from the iron and steel industry, modified slags, and a Si-rich product were tested using barley and pea as silicon accumulative and non-accumulative plants, respectively, at two application rates. The plants were grown under toxic concentrations of heavy metals in a greenhouse. Si-rich materials high in water-soluble Si had a positive effect at both the low and high application rates, and for both plant species. This type of substance can be regarded as Si fertilizer, demonstrating greater efficiency at a low application rate and lessened efficiency at a high application rate for protection of the cultivated plants against accumulation of the heavy metals.

     

The fractionation and geochemical characteristics of rare earth elements measured in ambient size-resolved PM in an integrated iron and steelmaking industry zone

Environmental Science and Pollution Research - Improved understanding of the fractionation and geochemical characteristic of rare earth elements (REEs) from steel plant emissions is important due...     

Healing the wounds in the landscape—reclaiming gravel roads in conservation areas

Reclaiming abandoned and unmaintained roads, built originally for forestry and mineral extraction, is an important part of ecological restoration, because the roads running through natural habitats cause fragmentation. The roads can be reclaimed in a passive way by blocking access to the road, but successful seedling recruitment may require additional management due to the physical constraints present at the road. We established a full factorial study to compare the effects of three road reclaiming measures, namely ripping, creation of safe sites by adding mulch and pine seed addition, on soil processes, recovery of understorey vegetation and seedling recruitment in three conservation areas in eastern Finland. We surveyed soil organic matter, frequency and cover of plant functional types, litter and mineral soil, and number of tree seedlings. The soil organic matter was, on average, 1.3-fold in the 50-cm-deep ripping treatment relative to unripped and 20-cm-deep ripping treatments. The germination and survival of deciduous seedlings and grass establishment were promoted by adding mulch. The addition of pine seeds counteracted the seed limitation and enhanced the regeneration of trees. The treatment combination consisting of ripping, adding mulch and pine seed addition enhanced the vegetation succession and tree-seedling recruitment most: the cover of grasses, herbs and ericaceous dwarf shrubs was 1.3–7.6-fold and the number of coniferous tree seedlings was 3.4–7.1-fold relative to the other treatment combinations. Differences between short-term (1–3 years) and longer-term (6 years) results indicate the need for a sufficient observation period in road reclamation studies.     

Estuarine circulation in the Taranto Seas

The Taranto basin is a shallow water marine system in the South of Italy characterized by the presence of a lagoon environment together with a semi-enclosed bay connected to the Ionian Sea. This marine system experienced over the last few decades strong biochemical pollution and environmental degradation, and it is considered a hotspot study site for economic, ecological and scientific reasons. The aim of this study was to examine, on an annual temporal scale and with high spatial resolution, the main hydrodynamical processes and transport scales of the system by means of a 3D finite element numerical model application, adopting the most realistic forcing available. The model allowed us to assess the role played by baroclinic terms in the basin circulation, describing its estuarine nature. In particular, the main features of water circulation, salinity and temperature distribution, water renewal time and bottom stress were investigated. Our results allowed us to equate this system dynamic to that of a weakly stratified estuary, identifying the main driving sources of this mechanism. The vertical stratification over the whole year was proved to be stable, leading to a dual circulation flowing out on the surface, mainly through Porta Napoli channel, and inflowing on the bottom mainly through Navigabile channel. This process was responsible also for the renewal time faster on the bottom of the Mar Piccolo basin than the surface. Due to the great importance of the Taranto basin for what concerns sediment pollution, also the effect of currents in terms of bottom stress was investigated, leading to the conclusion that only in the inlets area the values of bottom stress can be high enough to cause erosion.     

In situ immobilization of cadmium in soil by stabilized biochar-supported iron phosphate nanoparticles

The potential for nanoscale phosphate amendments to remediate heavy metal contamination has been widely investigated, but the strong tendency of nanoparticles to form aggregates limits the application of this technique in soil. This study synthesized a composite of biochar-supported iron phosphate nanoparticle (BC@Fe₃(PO₄)₂) stabilized by a sodium carboxymethyl cellulose to improve the stability and mobility of the amendment in soil. The sedimentation test and column test demonstrated that BC@Fe₃(PO₄)₂ exhibited better stability and mobility than iron phosphate nanoparticles. After 28 days of simulated in situ remediation, the immobilization efficiency of Cd was 60.2 %, and the physiological-based extraction test bioaccessibility was reduced by 53.9 %. The results of sequential extraction procedures indicated that the transformation from exchangeable (EX) Cd to organic matter (OM) and residue (RS) was responsible for the decrease in Cd leachability in soil. Accordingly, the pot test indicated that Cd uptake by cabbage mustard was suppressed by 86.8 %. Compared to tests using iron phosphate nanoparticles, the addition of BC@Fe₃(PO₄)₂ to soil could reduce the Fe uptake of cabbage mustard. Overall, this study revealed that BC@Fe₃(PO₄)₂ could provide effective in situ remediation of Cd in soil.