Black carbon (BC) plays a crucial role in sequestering hydrophobic organic contaminants in the environment. This study investigated key factors and mechanisms controlling nonideal sorption (e.g., sorption irreversibility and slow kinetics) of model hydrophobic organic contaminants (nitrobenzene, naphthalene, and atrazine) by rice-straw-derived BC. After removing the fraction of leachable pyrogenic organic carbon (LPyOC) (referring to composites of dissoluble non-condensed organic carbon and associated mineral components) with deionized water or 0.5 M NaOH, sorption of these sorbates to BC was enhanced. The sorption enhancement was positively correlated with sorbate molecular size in the order of atrazine > naphthalene > nitrobenzene. The removal of LPyOC also accelerated sorption kinetics and reduced sorption irreversibility. These observations were attributed to increased accessibility of BC micropores initially clogged by the LPyOC. Comparison of BC pore size distributions before and after atrazine sorption further suggested that the sorbate molecules preferred to access the micropores that were more open, and the micropore accessibility was enhanced by the removal of LPyOC. Consistently, the sorption of nitrobenzene and atrazine to template-synthesized mesoporous carbon (CMK3), a model sorbent with homogeneous pore structures, showed decreased kinetics, but increased irreversibility by impregnating sorbent pores with surface-grafted alkylamino groups and by subsequent loading of humic acid. These findings indicated an important and previously unrecognized role of LPyOC (i.e., micropore clogging) in the nonideal sorption of organic contaminants to BC.

This study sought to evaluate the toxicological effects of graphene oxide (GO) through tests with Danio rerio (zebrafish) embryos, considering the influence of the base washing treatment and the interaction with natural organic matter (i.e., humic acid, HA). A commercial sample of GO was refluxed with NaOH to remove oxidation debris (OD) byproducts, which resulted in a base washed GO sample (bw-GO). This process decreased the total oxygenated groups in bw-GO and its stability in water compared to GO. When tested in the presence of HA, both GO and bw-GO stabilities were enhanced in water. Although the embryo exposure showed no acute toxicity or malformation, the larvae exposed to GO showed a reduction in their overall length and acetylcholinesterase activity. In the presence of HA, GO also inhibited acid phosphatase activity. Our findings indicate a mitigation of material toxicity after OD removal. The difference in the biological effects may be related to the materials’ bioavailability and biophysicochemical interactions. This study reports for the first time the critical influence of OD on the GO material biological reactivity and HA interaction, providing new data for nanomaterial environmental risk assessment and sustainable nanotechnology.

Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils requires a higher microbial viability and an increased PAH bioavailability. The clay/modified clay-modulated bacterial degradation could deliver a more efficient removal of PAHs in soils depending on the bioavailability of the compounds. In this study, we modified clay minerals (smectite and palygorskite) with mild acid (HCl) and alkali (NaOH) treatments (0.5–3 M), which increased the surface area and pore volume of the products, and removed the impurities without collapsing the crystalline structure of clay minerals. In soil incubation studies, supplements with the clay products increased bacterial growth in the order: 0.5 M HCl ≥ unmodified ≥0.5 M NaOH ≥3 M NaOH ≥3 M HCl for smectite, and 0.5 M HCl ≥3 M NaOH ≥0.5 M NaOH ≥3 M HCl ≥ unmodified for palygorskite. A14C-tracing study showed that the mild acid/alkali-treated clay products increased the PAH biodegradation (5–8%) in the order of 0.5 M HCl ≥ unmodified > 3 M NaOH ≥ 0.5 M NaOH for smectite, and 0.5 M HCl > 0.5 M NaOH ≥ unmodified ≥ 3 M NaOH for palygorskite. The biodegradation was correlated (r = 0.81) with the bioavailable fraction of PAHs and microbial growth as affected particularly by the 0.5 M HCl and 0.5 M NaOH-treated clay minerals. These results could be pivotal in developing a clay-modulated bioremediation technology for cleaning up PAH-contaminated soils and sediments in the field.

One of the topics gaining lots of recent attention is the antimony (Sb) pollution. We have designed a dual-functional electroactive filter consisting of one-dimensional (1-D) titanate nanowires and carbon nanotubes for simultaneous oxidation and sorption of Sb(III). Applying an external limited DC voltage assist the in-situ conversion of highly toxic Sb(III) to less toxic Sb(V). The Sb(III) removal kinetics and efficiency were enhanced with flow rate and applied voltage (e.g., the Sb(III) removal efficiency increased from 87.5% at 0 V to 96.2% at 2 V). This enhancement in kinetics and efficiency are originated from the flow-through design, more exposed sorption sites, electrochemical reactivity, and limited pore size on the filter. The titanate-CNT hybrid filters perform effectively across a wide pH range of 3–11. Only negligible inhibition was observed in the presence of nitrate, chloride, and carbonate at varying concentrations. Our analyses using STEM, XPS, or AFS demonstrate that Sb were mainly adsorbed by Ti. DFT calculations suggest that the Sb(III) oxidation kinetics can be accelerated by the applied electric field. Exhausted titanate-CNT filters can be effectively regenerated by using NaOH solution. Moreover, the Sb(III)-spiked tap water generated ∼2400 bed volumes with a >90% removal efficiency. This study provides new insights for rational design of continuous-flow filters for the decontamination of Sb and other similar heavy metal ions.

The role of sediment–bound organic phosphorus (Pₒ) as an additional nutrient source is a component of internal P budgets in lake system that is usually neglected. Here we examined the relative importance of sediment Pₒ to internal P load and the role of bioavailable Pₒ in algal growth in Lake Erhai, China. Lake Erhai sediment extractable Pₒ accounted for 11–43% (27% average) of extractable total P, and bioavailable Pₒ accounted for 21–66% (40%) of Pₒ. The massive storage of bioavailable Pₒ represents an important form of available P, essential to internal loads. The bioavailable Pₒ includes mainnly labile monoester P and diester P was identified in the sequential extractions by H₂O, NaHCO₃, NaOH, and HCl. 40% of H₂O−Pₒ, 39% of NaHCO₃−Pₒ, 43% of NaOH−Pₒ, and 56% of HCl−Pₒ can be hydrolyzed to labile monoester and diester P, suggesting that the bioavailability of Pₒ fractions was in decreasing order as follows: HCl−Pₒ > NaOH−Pₒ > H₂O−Pₒ > NaHCO₃−Pₒ. It is implied that traditional sequential fractionation of Pₒ might overestimate the availability of labile Pₒ in sediments. Furthermore, analysis of the environmental processes of bioavailable Pₒ showed that the stabler structure of dissloved organic matter (DOM) alleviated the degradation and release of diester P, abundant alkaline phosphatase due to higher algal biomass promoted the degradation of diester P. The stability of DOM structure and the degradation of diester P might responsible for the spatial differences of labile monoester P. The biogeochemical cycle of bioavailable Pₒ replenishs available P pools in overlying water and further facilitate algal growth during the algal blooms. Therefore, to control the algal blooms in Lake Erhai, an effective action is urgently required to reduce the accumulation of Pₒ in sediments and interrupt the supply cycle of bioavailable Pₒ to algal growth.

The extensive use of reclaimed wastewater (RW) as a source of urban landscape pond replenishment, stimulated by the lack of surface water (SW) resources, has raised public concern. Greater attention should be paid to pond sediments, which act as ‘sinks’ and ‘sources’ of contaminants to the overlying pond water. Three ponds replenished with RW (RW ponds) in three Chinese cities were chosen to investigate 22 indices of sediment quality in four categories: eutrophication, heavy metal, ecotoxicity and pathogens risk. RW ponds were compared with other ponds of similar characteristics in the same cities that were replenished with SW (SW ponds). Our results show a strong impact of RW to the eutrophication and pathogenic risks, which are represented by organic matter, water content, total nitrogen, total phosphorus and phosphorus fractions, and pathogens. In particular, total phosphorus concentrations in the RW pond sediments were, on average, 50% higher than those of SW ponds. Moreover, the content of phosphorus, extracted by bicarbonate/dithionite (normally represented by BD-P) and NaOH (NaOH-P), were 2.0- and 2.83-times higher in RW ponds, respectively. For pathogens, the concentrations of norovirus and rotavirus in RW pond sediments were, on average, 0.52 and 0.30- log times those of SW ponds. The duration of RW replenishment was proved to have a marked impact on the eutrophication and pathogens risks from sediments. The continued use of RW for replenishment increases the eutrophication risk, and the pathogens risk, especially by viral pathogens, becomes greater.

Polycyclic aromatic hydrocarbons (PAHs), nicotine, cotinine, and metals in human hair have been used as important environmental exposure markers. We aimed to develop a simple method to simultaneously analyze these pollutants using a small quantity of hair. The digestion performances of tetramethylammonium hydroxide (TMAH) and sodium hydroxide (NaOH) for human hair were compared. Various solvents or their mixtures including n-hexane (HEX), dichloromethane (DCM) and trichloromethane (TCM), HEX:DCM32 (3/2) and HEX:TCM73 (7/3) were adopted to extract organics. The recoveries of metals were determined under an optimal operation of digestion and extraction. Our results showed that TMAH performed well in dissolving human hair and even better than NaOH. Overall, the recoveries for five solutions were acceptable for PAHs, nicotine in the range of 80%–110%. Except for HEX, other four extraction solutions had acceptable extraction efficiency for cotinine from HEX:TCM73 (88 ± 4.1%) to HEX:DCM32 (100 ± 2.8%). HEX:DCM32 was chosen as the optimal solvent in consideration of its extraction efficiency and lower density than water. The recoveries of 12 typical major or trace metals were mainly in the range of 90%–110% and some of them were close to 100%. In conclusion, the simultaneous analysis of PAHs, nicotine, cotinine, and metals was feasible. Our study provided a simple and low-cost technique for environmental epidemiological studies.

The main objective of this study was to unravel the chemical reactions and processes dictating the potential bioavailability of vanadium (V). In environmental solutions V exists in two stable oxidation states, +IV and +V, of which + V is considered to be more toxic. In this study, the effect of speciation and soil pH on the chemical accessibility of V was investigated with two soils: 1) field soil rather rich in soil organic matter (SOM) and 2) coarse mineral soil low in SOM. Fresh soil samples treated with V(+V) (added as NaVO3) or V(+IV) (added as VOSO4) (pH adjusted to the range 4.0–6.9) were incubated for 3 months at 22 °C. The adsorption tendency of V species was explored by water extraction (Milli-Q water, 1:50 dw/V) and by sequential extraction (0.25 M KCl; 0.1 M KH2/K2HPO4; 0.1 M NaOH; 0.25 M H2SO4, 1:10 dw/V). The potential bioavailability of V was found to be dictated by soil properties. SOM reduced V(+V) to V(+IV) and acted as a sorbent for both species, which lowered the bioaccessibility of V. A high pH, in turn, favored the predominance of the V(+V) species and thus increased the chemical accessibility of V.

In this study, Reverse phase dispersive liquid–liquid micro extraction (RP-DLLME) technique have been successfully developed to preconcentrate trace amount of phenol from sediment samples as a prior step to its derivatization with 4-aminoantipyrine and enhanced determination by UV–Vis spectrophotometry after primary ultrasonic extraction. In this procedure, 50μL 0.7M NaOH solution was chosen as extraction solvent and other factors including pH, extraction time, concentration of 4-aminoantipyrine, type and volume of dispersive solvents were optimized. Under selected conditions, the limit of detection, the linearity range, relative standard deviation and enrichment factor of method were obtained 15μg·kg−1, 50–1800μg·kg−1, 4.8% (n=10) and 33, respectively. Finally, using the high sensitivity, low organic solvent consumption and waste generation method, total phenol content in marine sediments from several locations in Chabahar Bay (southeast Iran) was estimated at 55.8–73.2μg·kg−1.

The present study verified the potential of volcanic rock powder residues originating from the extraction of semi-precious rocks in the state of Rio Grande do Sul, Brazil, as precursors or adsorbents for dyes and metallic ion removal from water. In this way, it is possible to add value and give an adequate destination to this waste. Volcanic rock powder residues from Ametista do Sul (AME) and Nova Prata (NP) were the starting materials. These were used naturally or submitted to the alkaline activation process at 60 °C and alkaline fusion at 550 °C. The analysis of the starting samples by X-ray fluorescence (XRF) revealed that they are mainly composed of aluminum, calcium, iron, and silicon oxides, which corroborates the presence of numerous crystalline phases observed in the X-ray diffraction spectra (XRD). Moreover, by XRD analysis of the synthesized samples, alkaline fusion proved to be more efficient in the dissolution of crystalline phases and consequently in the formation of the amorphous phase (more reactive). Furthermore, the adsorption tests with acid green and acid red dyes and Ag⁺, Co²⁺, and Cu²⁺ ions indicated the viability of using residual volcanic rock powder as raw material for the production of adsorbents functionalized with sodium hydroxide, being that the samples synthesized by alkaline fusion showed better results of removal and adsorption capacity for all the contaminants used in the study.