Neutral electrolyzed oxidizing water is effective for pre-harvest decontamination of fresh produce.

Pre-harvest sanitization of irrigation water has potential for reducing pathogen contamination of fresh produce. We compared the sanitizing effects of irrigation water containing neutral electrolyzed oxidizing water (EOW) or sodium hypochlorite (NaClO) on pre-harvest lettuce and baby spinach leaves artificially contaminated with a mixture of Escherichia coli, Salmonella Enteritidis and Listeria innocua (~1 × 108 colony-forming units/mL each resuspended in water containing 100 mg/L dissolved organic carbon, simulating a splash-back scenario from contaminated soil/manure). The microbial load and leaf quality were assessed over 7 days, and post-harvest shelf life evaluated for 10 days. Irrigation with water containing EOW or NaClO at 50 mg/L free chlorine significantly reduced the inoculated bacterial load by ≥ 1.5 log10, whereas tap water irrigation reduced the inoculated bacterial load by an average of 0.5 log10, when compared with untreated leaves. There were no visual effects of EOW or tap water irrigation on baby spinach or lettuce leaf surfaces pre- or post-harvest, whereas there were obvious negative effects of NaClO irrigation on leaf appearance for both plants, including severe necrotic zones and yellowing/browning of leaves. Therefore, EOW could serve as a viable alternative to chemical-based sanitizers for pre-harvest disinfection of minimally processed vegetables.

Silver Toxicity Thresholds for Multiple Soil Microbial Biomarkers.

Material flow analysis shows that soil is a key repository for silver (Ag) from (nano)silver-functionalized consumer products, but the potential effects of Ag toxicity, via Ag+ release, on soil microbial communities and their ecosystem services remains largely unknown. We examined the responses of multiple microbial biomarkers to increasing Ag+ doses (nine concentrations, 0-2000 mg kg-1) in nine different soils representing a wide range of soil properties. Analyses included substrate-induced microbial respiration, nine different soil enzyme activities, and quantification of bacterial 16S-rRNA (SSU) and fungal intergenic spacer (ITS) copies. The resulting half-maximal effective concentrations (EC50) for Ag ranged from ∼1 to >500 mg kg -1 and showed soil-specific responses, including some hormesis-type responses. Carbon cycle-associated enzyme activities (e.g., cellobiohydrolase, xylosidase, and α/ß-glucosidase) responded similarly to Ag. Sulfatase and leucine-aminopeptidase activities (linked to the sulfur and nitrogen cycles) were the most sensitive to Ag. Total organic carbon, and to a lesser extent pH, were identified as potentially useful response predictors, but only for some biomarkers; this reflects the complexity of soil Ag chemistry. Our results show Ag toxicity is highly dependent on soil characteristics and the specific microbial parameter under investigation, but end point redundancies also indicated that representative parameters for key microbial functions can be identified for risk assessment purposes. Sulfatase activity may be an important Ag toxicity biomarker; its response was highly sensitive and not correlated with that of other biomarkers.

In Situ Fixation of Metal(loid)s in Contaminated Soils: A Comparison of Conventional, Opportunistic, and Engineered Soil Amendments.

This study aimed to assess and compare the in vitro and in vivo bioaccessibility/bioavailability of As and Pb in a mining contaminated soil (As, 2267 mg kg(-1); Pb, 1126 mg kg(-1)), after the addition of conventional (phosphoric acid), opportunistic [water treatment residues (WTRs)], and engineered [nano- and microscale zero valent iron (ZVI)] amendments. Phosphoric acid was the only amendment that could significantly decrease Pb bioaccessibility with respect to untreated soil (41 and 47% in the gastric phase and 2.1 and 8.1% in the intestinal phases, respectively), giving treatment effect ratios (TERs, the bioaccessibility in the amended soil divided by the bioaccessibility in the untreated soil) of 0.25 and 0.87 in the gastric and intestinal phase, respectively. The in vivo bioavailability of Pb decreased in the phosphate treatment relative to the untreated soil (6 and 24%, respectively), and also in the Fe WTR 2% (12%) and nZVI-2 (13%) treatments. The ZVI amendments caused a decrease in As bioaccessibility, with the greatest decrease in the nZVI2-treated soil (TERs of 0.59 and 0.64 in the gastric and intestinal phases, respectively). Arsenic X-ray absorption near-edge spectroscopy analysis indicated that most of the As in the untreated soil was present as As(V) associated with Fe mineral phases, whereas in the treated soil, the proportion of arsenosiderite increased. Arsenite was present only as a minor species (3-5%) in the treated soils, with the exception of an nZVI treatment [∼14% of As(III)], suggesting a partial reduction of As(V) to As(III) caused by nZVI oxidation.

Copper toxicity on Eisenia fetida in a vineyard soil: a combined study with standard tests, genotoxicity assessment and gut metagenomic analysis.

Copper (Cu) toxicity is a pressing concern for several soils, especially in organic viticulture. The objective of this work was to assess Cu toxicity on the non-target organism Eisenia fetida, employing both traditional and novel tools for early identification of Cu-induced damages. In addition to traditional tests like avoidance and reproductive toxicity experiments, other tests such as the single cell gel electrophoresis (SCGE) and gut microbiome analysis were evaluated to identify early and more sensitive pollution biomarkers. Four sub-lethal Cu concentrations were studied, and the results showed strong dose-dependent responses by the earthworm avoidance test and the exceeding of habitat threshold limit at the higher Cu doses. An inverse proportionality was observed between reproductive output and soil Cu concentration. Bioaccumulation was not detected in earthworms; soil concentrations of potentially bioavailable Cu were not affected by E. fetida presence or by time. On the contrary, the SCGE test revealed dose-dependent genotoxicity for the 'tail length' parameter already at the second day of Cu exposition. Gut microbiome analysis a modulation of microbial composition, with the most aboundant families being Pectobateriaceae, Comamonadaceae and Microscillaceae. Bacillaceae increased over time and showed adaptability to copper up to 165 mg/kg, while at the highest dose even the sensitive Acetobacteriaceae family was affected. The research provided new insights into the ecotoxicity of Cu sub-lethal doses highlighting both alterations at earthworms' cellular level and changes in their gut microbiota.

Retzius-sparing Robot-assisted Simple Prostatectomy: Perioperative and Short-term Functional Outcomes Assessed via Validated Questionnaires.

Background and objective: Several surgical procedures have been reported for treatment of male patients with lower urinary tract symptoms (LUTS) secondary to large benign outlet obstruction (BOO). The diffusion of robotic surgery offers the possibility to perform open simple prostatectomy (SP) with a minimally-invasive approach. Our aim was to report outcomes of the Retzius-sparing robot-assisted SP (RS-RASP) technique. Methods: This was a single centre, prospective study. Patients with LUTS secondary to BOO and a prostate volume of >100 ml underwent RS-RASP performed with a da Vinci surgical system in four-arm configuration for a transperitoneal approach. Data for intraoperative and perioperative complications were collected. Functional outcomes were assessed via validated patient questionnaires. Univariable and multivariable regression analyses were used to identify predictors of complications and achievement of a trifecta composite outcome. Key findings and limitations: The median patient age was 69 yr and the median prostate volume was 150 ml. The median operative time was 175 min, with estimated blood loss of 350 ml. The median in-hospital stay and median catheterisation time were 3 d and 9 d, respectively. Within 90 d, the incidence of complications was 3% for grade 1, 19% for grade 2, and 2% for grade 3 complications. At 7-mo follow-up, statistically significant improvements in International Prostate Symptom Scores (total score and quality of life), International Consultation on Incontinence Questionnaire-Urinary Incontinence Short Form (ICIQ-UI SF) scores, and the maximum flow rate were observed (all p < 0.0001). According to ICIQ-UI SF scores, 20%, 6%, and 3% of the patients had slight, moderate, or severe urinary incontinence (UI), respectively. Urgency UI was experienced by 14% of the patients and stress UI by 10%. Most of the patients with UI reported leakage of a small amount of urine and they did not wear pads. Conclusions: RS-RASP was associated with good perioperative outcomes and a low prevalence of high-grade complications. Significant LUTS relief was achieved, but some patients experienced slight urgency or stress UI at short-term follow-up. Patient summary: We explored a surgical technique called Retzius-sparing robot-assisted simple prostatectomy to treat men with bothersome urinary symptoms caused by a large prostate. The technique led to good results, with minimal bleeding and few complications during surgery. This surgery could be a beneficial choice for patients with stubborn urinary symptoms and a large prostate gland.

Effects of chemical amendments on the lability and speciation of metals in anaerobically digested biosolids.

The interaction of inorganic contaminants present in biosolids with iron, aluminum, and manganese oxy/hydroxides has been advocated as a key mechanism limiting their bioavailability. In this study, we investigated whether this is indeed the case, and further, whether it can be exploited to produce optimized biosolids products through the addition of chemical additives during sewage sludge processing. Experiments were conducted to investigate whether the addition of iron- and aluminum-based amendments (at 5 different rates) during the anaerobic digestion phase of wastewater treatment can effectively change the speciation or lability of contaminant metals (copper, zinc and cadmium) in biosolids destined for use in agriculture. The performance of the bioreactors was monitored throughout and the speciation and lability were determined in both fresh and 3-month aged biosolids using X-ray absorption spectroscopy (Cu, Zn) and isotopic dilution ((65)Cu, (65)Zn, (109)Cd). The tested amendments (FeCl3, Al2(SO4)3, and Al-rich water treatment residual) did not cause significant changes in metal speciation and were of limited use for reducing the lability of contaminant metals in good quality biosolids (suitable for use in agriculture), suggesting that high affinity binding sites were already in excess in these materials. However, the use of chemical amendments may offer advantages in terms of treatment process optimization and may also be beneficial when biosolids are used for contaminated site remediation.

Surface immobilization of engineered nanomaterials for in situ study of their environmental transformations and fate.

The transformation and environmental fate of engineered nanomaterials (ENMs) is the focus of intense research due to concerns about their potential impacts in the environment as a result of their uniquely engineered properties. Many approaches are being applied to investigate the complex interactions and transformation processes ENMs may undergo in aqueous and terrestrial environments. However, major challenges remain due to the difficulties in detecting, separating, and analyzing ENMs from environmental matrices. In this work, a novel technique capable of in situ study of ENMs is presented. By exploiting the functional interactions between surface modified silver nanoparticles (AgNPs) and plasma-deposited polymer films, AgNPs were immobilized on to solid supports that can be deployed in the field and retrieved for analysis. Either negatively charged citrate or polyethylene glycol, or positively charged polyethyleneimine were used to cap the AgNPs, which were deployed in two field sites (lake and marina), two standard ecotoxicity media, and in primary sewage sludge for a period of up to 48 h. The chemical and physical transformations of AgNPs after exposure to different environments were analyzed by a combination of XAS and SEM/EDX, taken directly from the substrates. Cystine- or glutathione-bound Ag were found to be the dominant forms of Ag in transformed ENMs, but different extents of transformation were observed across different exposure conditions and surface charges. These results successfully demonstrate the feasibility of using immobilized ENMs to examine their likely transformations in situ in real environments and provide further insight into the short-term fate of AgNPs in the environment. Both the advantages and the limitations of this approach are discussed.

Application of native plants in constructed floating wetlands as a passive remediation approach for PFAS-impacted surface water.

Strategies for remediation of per- and polyfluoroalkyl substances (PFAS) generally prioritise highly contaminated source areas. However, the mobility of PFAS in the environment often results in extensive low-level contamination of surface waters across broad areas. Constructed Floating Wetlands (CFWs) promote the growth of plants in buoyant structures where pollutants are assimilated into plant biomass. This study examined the hydroponic growth of Juncus krausii, Baumea articulata and Phragmites australis over a 28-day period for remediation of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) contaminated (0.2 µg/L to 30 µg/L) urban stormwater. With increasing PFOA and PFOS concentrations, accumulation in plant species increased although root and shoot distribution varied depending on PFAS functional group. Less PFOA than PFOS accumulated in plant roots (0.006-0.16 versus 0.008-0.68 µg/g), while more PFOA accumulated in the plant shoots (0.02-0.55 versus 0.01-0.16 µg/g) indicating translocation to upper plant portions. Phragmites australis accumulated the highest overall plant tissue concentrations of PFOA and PFOS. The NanoSIMS data demonstrated that PFAS associated with roots and shoots was absorbed and not just surface bound. These results illustrate that CFWs have the potential to be used to reduce PFAS contaminants in surface waters.

Effect of soil amendments on molybdenum availability in mine affected agricultural soils.

Molybdenum (Mo) contamination of agricultural soils around Mo-mining areas is of emerging environmental concern. This study evaluated potential practical techniques for chemical immobilization of three Mo contaminated agricultural soils via application of up to six amendments from four different types of materials including biosolids, biochar supported nanoscale zero-valent iron (BC-nZVI), drinking water treatment residues (WTR) and ferrous minerals (magnetite and ferrihydrite). The efficacy of the different amendments on soil Mo bioaccessibility and bioavailability was evaluated by monitoring Mo uptake in both monocotyledon (ryegrass) and dicotyledon (alfalfa) plants, soil extractable Mo, and Mo bioavailability as measured by Diffusive Gradient in Thin Films (DGT®). All amendments exhibited no immobilization effect and increased Mo extractability in the severely contaminated soil (264 mg Mo kg-1). In contrast, in lightly and moderately contaminated soils (22 and 98 mg Mo kg-1), biosolids, WTR and magnetite all reduced soil extractable Mo and decreased Mo uptake in both alfalfa and ryegrass shoots relative to controls (CK). Moreover, DGT showed that during incubation experiments while biosolids amendments increased Mo bioavailability from 115 to 378% compared to the CK treatments, all other amendments decreased Mo bioavailability insignificantly.

Insights into the fate of antimony (Sb) in contaminated soils: Ageing influence on Sb mobility, bioavailability, bioaccessibility and speciation.

The effect of long-term ageing (up to 700 days) on the mobility, potential bioavailability and bioaccessibility of antimony (Sb) was investigated in two soils (S1: pH 8.2; S2: pH 4.9) spiked with two Sb concentrations (100 and 1000 mg·kg-1). The Sb mobility decreased with ageing as highlighted by sequential extraction, while its residual fraction significantly increased. The concentration of Sb (CDGT), as determined by diffusive gradients in thin films (DGT), showed a reduction in potential contaminant bioavailability during ageing. The DGT analysis also showed that Sb-CDGT after 700 days ageing was significantly higher in S1-1000 compared to S2-1000, suggesting soil pH plays a key role in Sb potential bioavailability. In-vitro tests also revealed that Sb bioaccessibility (and Hazard Quotient) decreased over time. Linear combination fitting of Sb K-edge XANES derivative spectra showed, as a general trend, an increase in Sb(V) sorption to inorganic oxides with ageing as well as Sb(V) bound to organic matter (e.g. up to 27 and 37% respectively for S2-100). The results indicated that ageing can alleviate Sb ecotoxicity in soil and that the effectiveness of such processes can be increased at acidic pH. However, substantial risks due to Sb mobility, potential bioavailability and bioaccessibility remained in contaminated soils even after 700 days ageing.

Inactivation, removal, and regrowth potential of opportunistic pathogens and antimicrobial resistance genes in recycled water systems.

With two thirds of the global population living in areas affected by water scarcity, wastewater reuse is actively being implemented or explored by many nations. There is a need to better understand the efficacy of recycled water treatment plants (RWTPs) for removal of human opportunistic pathogens and antimicrobial resistant microorganisms. Here, we used a suite of probe-based multiplex and SYBR green real-time PCR assays to monitor enteric opportunistic pathogens (EOPs; Acinetobacter baumannii, Arcobacter butzlieri, Escherichia coli, Enterococcus faecalis, Klebsiella pneumoniae, Legionella spp., Listeria monocytogenes, Pseudomonas aeruginosa, Salmonella Enteritidis, Streptococcus spp.) and antimicrobial resistance genes (ARGs; qnrS, blaSHV, blaTEM, blaGES, blaKPC, blaIMI, blaSME, blaNDM, blaVIM, blaIMP, blaOXA-48-like, mcr-1 and mcr-3) of key concern from an antimicrobial resistance (AMR), waterborne and foodborne disease perspective. The class 1 integron-integrase gene (intl1) was quantified as a proxy for multi-drug resistance. EOPs, intl1 and ARGs absolute abundance (DNA and RNA) and metabolic activity (RNA) was assessed through three RWTPs with differing treatment trains. Our results indicate that RWTPs produced high quality recycled water for non-potable reuse by removing >95% of EOPs and ARGs, however, subpopulations of EOPs and ARGs survived disinfection and demonstrated potential to become actively growing members of the recycled water and distribution system microbiomes. The persistence of functional intl1 suggests that significant genetic recombination capacity remains in the recycled water, along with the likely presence of multi-drug resistant bacteria. Results provide new insights into the persistence and growth of EOPs, and prevalence and removal of ARGs in recycled water systems. These data will contribute towards the emerging evidence base of AMR risks in recycled water to inform quantitative risk-based policy development regarding water recycling schemes.

Plant-Available Phosphorus in Highly Concentrated Fertilizer Bands: Effects of Soil Type, Phosphorus Form, and Coapplied Potassium.

Phosphorus (P) is increasingly being applied in concentrated bands to satisfy plant nutrient requirements. To quantify changes in plant-available P in the fertosphere of highly concentrated fertilizer bands, we conducted a soil-fertilizer incubation experiment using seven soil types, three highly water-soluble P sources [monocalcium phosphate (MCP), monoammonium phosphate (MAP), and diammonium phosphate (DAP)], and coapplication of potassium chloride (KCl). First, we found that soil properties were important in influencing P availability. For a calcareous soil, availability was generally low irrespective of treatment, presumably due to precipitation of the fertilizer as Ca-P minerals. For all six noncalcareous soils, fertosphere pH was critical in determining potential P availability, with decreasing pH values decreasing availability, presumably due to precipitation of Al- and Fe-P minerals. Second, given the importance of pH, we also found that the form of P supplied (MCP, MAP, or DAP) had a pronounced effect on P availability due to associated changes in fertosphere pH. Finally, we also found that the coapplication of K also decreased P availability in some soils. We conclude that the selection of the P source is of utmost importance when fertilizers are placed as highly concentrated bands and that soil properties also need to be considered.

Chemical characterisation, antibacterial activity, and (nano)silver transformation of commercial personal care products exposed to household greywater.

The objective of this study was to test the original speciation of silver (Ag) in eight different commercially available personal care products and investigate the chemical transformation of Ag during exposure to two types of synthetic greywater. The antimicrobial activity of the products was examined to determine the relationship between Ag content and speciation with the antibacterial functionality of the products. The Ag content of each product was quantified and X-ray absorption near-edge structure (XANES) analysis was used to investigate the initial speciation in the products and the changes occurring upon mixture with greywater. The results showed that the total Ag concentration in the products ranged from 17 to 30 mg kg-1, and was usually below the value reported on the label. Analyses revealed the complexity of Ag speciation in these products and highlighted the importance of characterisation studies to help elucidate the potential risks of nano-Ag in the environment. The antibacterial results confirmed that the antibacterial efficacy of the products depends on the concentration, form and speciation of Ag in the products, but is also significantly affected by product formulation. For instance, many of the products contained additional bactericidal ingredients, making it difficult to determine how much of the bactericidal effect was due directly to the Ag content/species. This paper offers some suggestions for standard methodologies to facilitate cross-comparison of potential risks across different studies and nano-enabled products.

Comparative antibacterial activities of neutral electrolyzed oxidizing water and other chlorine-based sanitizers.

There is increasing demand for safe and effective sanitizers for irrigation water disinfection to prevent transmission of foodborne pathogens to fresh produce. Here we compared the efficacy of pH-neutral electrolyzed oxidizing water (EOW), sodium hypochlorite (NaClO) and chlorine dioxide (ClO2) against single and mixed populations of E. coli, Listeria and Salmonella under a range of pH and organic matter content. EOW treatment of the mixed bacterial suspension resulted in a dose-dependent (<1 mg/L free chlorine), rapid (<2 min) and effective (4-6 Log10) reduction of the microbial load in water devoid of organic matter under the range of pH conditions tested (pH, 6.0, 7.0, 8.4 and 9.2). The efficacy of EOW containing 5 mg/L free chlorine was unaffected by increasing organic matter, and compared favourably with equivalent concentrations of NaClO and ClO2. EOW at 20 mg/L free chlorine was more effective than NaClO and ClO2 in reducing bacterial populations in the presence of high (20-100 mg/L) dissolved organic carbon, and no regrowth or metabolic activity was observed for EOW-treated bacteria at this concentration upon reculturing in rich media. Thus, EOW is as effective or more effective than other common chlorine-based sanitizers for pathogen reduction in contaminated water. EOW's other characteristics, such as neutral pH and ease of handling, indicate its suitability for fresh produce sanitation.

A Facultative Electroactive Chromium(VI)-Reducing Bacterium Aerobically Isolated From a Biocathode Microbial Fuel Cell.

A facultative electroactive bacterium, designated strain H, was aerobically isolated from the biocathode of a hexavalent chromium (Cr(VI))-reducing microbial fuel cell (MFC). Strain H is Gram-positive and rod shaped (1-3 µm length). 16S rRNA gene analysis suggested that this strain (accession number MH782060) belongs to the genus Bacillus and shows maximum similarity to Bacillus cereus whose electrochemical activity has never previously been reported. Moreover, this strain showed efficient Cr(VI)-reducing ability in both heterotrophic (aerobic LB broth) and autotrophic (anaerobic MFC cathode) environments. Cr(VI) removal reached 50.6 ± 1.8% after 20 h in LB broth supplemented with Cr(VI) (40 mg/L). The strain H biocathode significantly improved the performance of the Cr(VI)-reducing MFC, achieving a maximum power density of 31.80 ± 1.06 mW/m2 and Cr(VI) removal rate of 2.56 ± 0.10 mg/L-h, which were 1.26 and 1.75 times higher than those of the MFC with the sterile control cathode, respectively. This study offers a novel Gram-positive Bacillus sp. strain for Cr(VI) removal in MFCs, and shows a facile aerobic isolation method could be used to screen facultative electroactive bacteria.

Anode modification by biogenic gold nanoparticles for the improved performance of microbial fuel cells and microbial community shift.

In this study, carbon cloth anodes were modified using biogenic gold nanoparticles (BioAu) and nanohybrids of multi-walled carbon nanotubes blended with BioAu (BioAu/MWCNT) to improve the performance of microbial fuel cells (MFCs). The results demonstrated that BioAu modification significantly enhanced the electricity generation of MFCs. In particular, BioAu/MWCNT nanohybrids as the modifier displayed a better performance. The MFC with the BioAu/MWCNT electrode had the shortest start-up time (6.74 d) and highest power density (178.34 ±â€¯4.79 mW/m2), which were 141.69% shorter and 56.11% higher compared with those of the unmodified control, respectively. These improvements were attributed to the excellent electrocatalytic activity and strong affinity towards exoelectrogens of the BioAu/MWCNT nanohybrids on the electrode. High throughput sequencing analysis indicated that the relative abundance of electroactive bacteria in the biofilm community, mostly from the classes of Gammaproteobacteria and Negativicutes, increased after anode modification.

Essential oil diversity of Origanum vulgare L. populations from Southern Italy.

Essential oils (EOs) belonging to 25 wild populations of Origanum vulgare L. samples, growing wild in different locations of Calabria Region (Southern Italy), were analyzed using gas chromatography-mass spectrometry. The quantitative and qualitative data showed EO concentrations ranging from 0.96 to 5.10% and 37 compounds detected, representing more than 80% of the total composition of the oils. By applying hierarchical cluster analysis on the basis of the EO constituents, two main groups and three subgroups were found, reflecting the variation in the chemical composition of EOs from wild oregano populations. The first group consisted of acyclic (linalool/linalyl acetate) chemotypes with a predominant presence of linalyl acetate; the second was characterized by chemotypes rich in cymyl-compounds, mainly carvacrol, thymol and γ-terpinene. The data obtained contribute to broaden the inventory of wild oregano populations from Calabria to plan programs for the selection of chemotypes with new and specific uses.

Sorption of silver nanoparticles to laboratory plastic during (eco)toxicological testing.

Here, we evaluate the extent of sorption of silver nanoparticles (AgNPs) with different primary sizes (30 and 70 nm) and surface properties (branched polyethylene imine, "bPEI" and citrate coating) to laboratory plastic during (eco)toxicological testing. Under conditions of algal growth inhibition assay, up to 97% of the added AgNPs were sorbed onto the test vessels whereas under conditions of in vitro toxicological assay with mammalian cells, the maximum loss of AgNPs was 15%. We propose that the high concentration of proteins and biomolecules in the in vitro toxicological assay originating from serum-containing cell culture medium prevented NP sorption due to steric stabilisation. The sorption of AgNPs to test vessels was clearly concentration dependent. In the conditions of algal growth inhibition assay at 10 ng AgNPs/mL, up to 97% of AgNPs were lost from the test while at higher concentrations (1000 ng AgNPs/mL), the loss of AgNPs was remarkably smaller, up to 64%. Sorption of positively charged bPEI-coated AgNPs was more extensive than the sorption of negatively charged citrate-coated AgNPs and, when calculated on a mass basis, more 70 nm-sized Ag than 30 nm Ag sorbed to plastic surfaces. In summary, this study demonstrates that the loss of AgNPs during (eco)toxicological tests due to sorption on test vessel surfaces is significant, especially in diluted media (e.g. in algal growth medium) and at low NP concentrations. Thus, to ensure the accurate interpretation of (eco)toxicological results, the loss of AgNPs due to adsorption to test vessels should not be overlooked and considered for each specific case.

Fate of zinc and silver engineered nanoparticles in sewerage networks.

Engineered zinc oxide (ZnO) and silver (Ag) nanoparticles (NPs) used in consumer products are largely released into the environment through the wastewater stream. Limited information is available regarding the transformations they undergo during their transit through sewerage systems before reaching wastewater treatment plants. To address this knowledge gap, laboratory-scale systems fed with raw wastewater were used to evaluate the transformation of ZnO- and Ag-NPs within sewerage transfer networks. Two experimental systems were established and spiked with either Ag- and ZnO-NPs or with their dissolved salts, and the wastewater influent and effluent samples from both systems were thoroughly characterised. X-ray absorption spectroscopy (XAS) was used to assess the extent of the chemical transformation of both forms of Zn and Ag during transport through the model systems. The results indicated that both ZnO- and Ag-NPs underwent significant transformation during their transport through the sewerage network. Reduced sulphur species represented the most important endpoint for these NPs in the sewer with slight differences in terms of speciation; ZnO converted largely to Zn sulfide, while Ag was also sorbed to cysteine and histidine. Importantly, both ionic Ag and Ag-NPs formed secondary Ag sulfide nanoparticles in the sewerage network as revealed by TEM analysis. Ag-cysteine was also shown to be a major species in biofilms. These results were verified in the field using recently developed nanoparticle in situ deployment devices (nIDDs) which were exposed directly to sewerage network conditions by immersing them into a municipal wastewater network trunk sewer and then retrieving them for XAS analysis.