The Transformation of Inorganic and Methylmercury in the Presence of l-Cysteine Capped CdSe Nanoparticles

Transformations of mercury (Hg) forms in the aquatic environment is a crucial aspect of Hg fate, transport and the bioaccumulation of methylmercury (CH3Hg; MeHg), which is the form that drives most human health concerns. Transformations between Hg forms on surfaces have been inadequately studied but here we report on the interaction of inorganic Hg (HgII) and MeHg with chalcogenide nanoparticles (NPs); specifically L-cysteine capped CdSe nanocrystals. The study sheds light on the transformation of the Hg species and the interaction mechanisms, by examining the product composition, reaction mass balance and the distribution between the liquid and solid phase. The results showed that the quenching of the photoluminescence (PL) of CdSe NPs was greater for HgII than MeHg, and that HgII caused significant PL quenching even when its concentration was in the nM range. Over 90% of HgII was found associated with the solid phase while most MeHg existed in the liquid phase in the experimental solutions. No dimethylmercury ((CH3)2Hg; DMeHg) was produced from the interaction of MeHg and the NPs, in contrast to findings with microparticles. However, a fast and complete MeHg transformation into HgII occurred when the MeHg + NPs mixture was exposed to light. A scheme for the MeHg degradation was derived and is presented, and it was concluded that the precipitation of HgSe accelerated the MeHg degradation. These results provide insight into the abiotic pathways for MeHg degradation in environmental waters in the presence of NPs.

Fate and Toxicity of Carbamazepine and Its Degradation By-Products During Coupling of Ozonation and Nanofiltration for Urban Wastewater Reuse

Occurrence of emerging organic micropollutants in water bodies and their effects are a concern related to quality of reused water. Advanced oxidation processes have demonstrated promising results to address this challenge. Nonetheless, these processes may lead to the generation of more toxic oxidation by-products. The aim of this study was to investigate the coupling of ozonation and nanofiltration (NF) applied to carbamazepine (CBZ). It consisted in monitoring the degradation and fate of CBZ and its subsequent by-products, their fate and toxicity. CBZ was completely degraded after 5 min of ozonation and six identified transformation by-products were formed: I (hydroxycarbamazepine), BQM [1-(2-benzaldehyde)-4-hydro-(1H, 3H)-quinazoline-2-one], II (2-(1H)-quinazolinone), BaQM [1-(2-benzoic acid)-4-hydro-(1H, 3H)-quinazoline-2-one], BQD [1-(2-benzaldehyde)-(1H, 3H)-quinazoline-2,4-dione] and BaQD [1-(2-benzoic acid)-(1H, 3H)-quinazoline-2,4-dione]. Mineralization rate of ozonation never exceeded 12% even with high ozone dose. Bioassays with Vibrio fischeri revealed that BQM and BQD are responsible for toxicity. NF is able to remove total organic carbon with removal rate up to 93% at 85% of permeate recovery rate. CBZ and its different ozonation by-products were almost completely retained by NF, except the II, which had an MW slightly lower than the membrane molecular weight cut-off, for which the removal rate was still between 80 and 96% depending on the recovery rate.

Sr Isotopic Composition of NIES Certified Reference Material No. 28 Urban Aerosols

An interlaboratory study of the National Institute for Environmental Studies (NIES) certified reference material (CRM) No. 28 Urban Aerosols collected from the filters of a central ventilating system in a building in the Beijing city center from 1996 to 2005 was performed to obtain an information value of the Sr isotopic composition. The Sr isotopic composition was measured using multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) to confirm the CRM’s within- and between-bottle homogeneity, and the results showed a 87Sr/86Sr ratio of 0.710227 ± 0.000019 (2SD, n = 18). The Sr isotopic compositions were intercompared using thermal ionization mass spectrometry (TIMS), which showed good agreement with values obtained at NIES. Subsequently, a consistent 87Sr/86Sr ratio was observed between two dissolution (hotplate vs. high-pressure bomb) and Sr separation (Sr spec resin vs. cation exchange resin) methods. To validate and reproduce the accuracy of our analytical methods, the Sr isotopic compositions of secondary reference materials, JB-1b and JA-2, were also measured. Our results showed that NIES CRM No. 28 is appropriate for the quality control of Sr isotope measurements of particulate matter analyses for environmental and geochemical studies.

Amino-Thiol Bifunctional Polysilsesquioxane/Carbon Nanotubes Magnetic Composites as Adsorbents for Hg(II) Removal

Amino-thiol bifunctional polysilsesquioxane/carbon nanotubes (PSQ/CNTs) magnetic composites were prepared by sol-gel method with two types of functional siloxanes coating on carboxyl CNTs simultaneously. The composites were served as efficient adsorbents for removing Hg(II) in aqueous solution and the adsorption properties were investigated systematically. The optimal pH of bifunctional composites for Hg(II) removal is at pH 4.5. The thermodynamic fitting curves are more consistent with the Langmuir model and the adsorption capacities of the bifunctional composites for Hg(II) varied from 1.63 to 1.94 mmol g−1 at 25°C according to the Langmuir model. The kinetics curves are more fitted to the pseudo-second-order model and the composites could selectively adsorb Hg(II) in a series of binary metal ions solution. The elution regeneration tests showed that the adsorption rate could still reach 78% after repeat cycle three times. It is expected that the bifunctional PSQ/CNTs magnetic composites can be potentially applied to remove low concentration Hg(II) from waste water.

In-Situ FTIR Study of Heterogeneous Oxidation of SOA Tracers by Ozone

Secondary organic aerosols (SOA) play an important role in global climate change and air quality, and SOA tracers can directly characterize the source and reaction mechanism of SOA. However, it is not well known that whether the tracers can be oxidized or how the instability of the tracers in the atmosphere. In this paper, in-situ FTIR was used to analyze the chemical structure changes of erythritol, analogue of 2-methyl erythritol (AME) that is, a tracer of isoprene SOA, and 2, 3-dihydroxy-4-oxopentanoic acid (DHOPA), a tracer of toluene SOA, when exposed to high concentration of ozone for short periods. Under the condition of 20 ppm ozone exposure for 30 min, the change rate of absorption area of AME at 3,480 and 1700 cm−1 was −0.0134 and 0.00117 int.abs/s, respectively, and the change rate of the absorption area of DHOPA at 1,640 and 3340cm−1 was −0.00191 and 0.00218 int.abs/s, respectively. The pseudo-first-order reaction rate constant kapp were 1.89 × 10−8 and 2.12 × 10−7 s−1, and the uptake coefficients of ozone on the surface of AME and DHOPA were (1.3 ± 0.8) × 10−8 and (4.5 ± 2.7) × 10−8, respectively. These results showed the oxidation processes of AME and DHOPA were slow in the presence of high concentrations of ozone, which implied that AME and DHOPA could be considered to be stable in the atmospheric environment with ozone as the main oxidant.

Environmental Fate and Behavior of the Herbicide Glyphosate in Sandy Soils of Florida Under Citrus Production

Chemical weed control using herbicide glyphosate to manage emerged weeds is an important production practice in Florida citrus. Despite the extensive use of glyphosate in citrus orchards, very limited information is available on its environmental fate and behavior in Florida soils that are predominantly sandy in nature. Hence, the study’s objective was to understand the adsorption-desorption, dissipation dynamics, and vertical movement or leaching of glyphosate in sandy soils in citrus orchards. Laboratory, field, and greenhouse experiments were conducted at Southwest Florida Research and Education Center in Immokalee, Florida. The adsorption-desorption behavior of glyphosate in the soils from three major citrus production areas in Florida was studied utilizing a batch equilibrium method. The dissipation of glyphosate was tracked in the field following its application at the rate of 4.20 kg ae ha−1. Soil leaching columns in greenhouse conditions were used to study the vertical movement of glyphosate. The results suggest that glyphosate has a relatively lower range of adsorption or binding (Kads = 14.28–30.88) in the tested soil types. The field dissipation half-life (DT50) of glyphosate from surface soil was found to be ∼26 days. Glyphosate moved vertically or leached into the soil profile, up to 40 cm in the soil column, when analyzed 40 days after herbicide application. The primary degradation product of glyphosate, i.e., aminomethyl phosphonic acid (AMPA), was also detected up to the depth of 30 cm below the soil surface, indicating the presence of microbial metabolism of glyphosate in the soil.

The Effect of Heterogeneity on the Distribution and Treatment of PFAS in a Complex Geologic Environment

Per-and polyfluoroalkyl substances (PFAS) have been identified as emerging contaminants of concern in the environment in a wide variety of media including groundwater. Typically, PFAS-impacted groundwater is extracted by pump and treat systems and treated using sorptive media such as activated carbon and ion exchange resin. Pump and treat systems are generally considered ineffective for the remediation of dissolved phase contaminants including PFAS but instead are considered applicable for plume containment. An alternative to pump and treat is in-situ treatment. The demonstrated use of in-situ treatment for PFAS-impacted groundwater is limited with only colloidal activated carbon (CAC) being shown to effectively attenuate PFAS over short and moderate time periods. Active research topics for the in-situ treatment of PFAS include the effect of heterogeneity on the distribution of the CAC, the lifespan of the CAC itself, the effect of competitive adsorption/absorption, and the effect of other geochemical conditions on the removal process. This study looked at the effect of heterogeneity on the distribution of CAC and subsequent treatment of PFAS at a site with a multiple aquifer system. The site’s geology varied from a silty sand to sand to fractured bedrock with all three units being impacted by PFAS and benzene (B), toluene (T), ethylbenzene (E), and xylene (X). Parameters evaluated included the distribution of the CAC as well as the subsequent treatment of the PFAS and BTEX. Results of groundwater sampling indicated that the PFAS detected within the groundwater were treated effectively to below their respective reporting limits for the duration of the 1-year test in both the silty sand and sand aquifers. The PFAS in the fractured rock aquifer showed a different treatment profile with longer carbon chained PFAS being attenuated preferentially compared to the shorter carbon chained PFAS. These results suggest that competitive sorptive reactions were occurring on the CAC within the fractured rock. Analysis of the unconsolidated aquifer materials determined that direct push injection of the CAC was effective at delivering the CAC to the target injection zones with post-injection total organic carbon (TOC) concentrations increasing by up to three orders of magnitude compared to pre-injection TOC concentrations. Heterogeneity did have an impact on the CAC distribution with higher hydraulic conductivity zones receiving more CAC mass than lower hydraulic conductivity zones.

Interferences and Matrix Effects on Iron Isotopic Composition Measurements by 57Fe-58Fe Double-Spike Multi-Collector Inductively Coupled Plasma Mass Spectrometry; the Importance of Calcium and Aluminum Interferences

Multi-collector inductively coupled plasma mass spectrometers (MC-ICPMS) are widely used for Fe isotope measurements. The latter may be perturbed by interferences (notably from Cr and Ni) and matrix effects (notably from major elements), caused by elements remaining in the samples after purification. We quantified some of these perturbations and our ability to correct them whenever possible, using Thermo Neptune and Neptune Plus MC-ICPMS with a 57-58Fe double-spike mass bias correction. 54Cr and 58Ni isobaric interference corrections were found to be extremely efficient up to Cr/Fe=0.12 and Ni/Fe=0.04 (g/g natural Fe). Matrix effects were found negligible up to at least Na/Fe=175, Mg/Fe=10, K/Fe=1.5, and Mo/Fe=75 (g/g natural Fe). 28Si2+ interference was found negligible up to Si/Fe=50. Finally, we found that calcium and aluminum could cause significant interferences (e.g., 40Ca16O and 27Al2+), for Ca/Fe ≥ 2.5 and Al/Fe ≥ 2.5. The perturbation intensity relative to the Ca/Fe ratio was found dependent on the measurement conditions (plateau width). While working with samples with potentially high calcium or aluminum contents (such as calcite minerals or tests, bones and teeth, or marine samples and crustal rocks), we recommend to carefully take into account Ca and Al while tuning the instrument and checking the measurement accuracy with isotopic standards (i.e., doping the isotopic standard with Ca and Al levels comparable to those of the samples).