Vertical distribution of microplastics in an agricultural soil after long-term treatment with sewage sludge and mineral fertiliser

Sewage sludge applications release contaminants to agricultural soils, such as potentially toxic metals and microplastics (MPs). However, factors determining the subsequent mobility of MPs in long-term field conditions are poorly understood. This study aimed to understand the vertical distribution of MPs in soils amended with sewage sludge in comparison to conventional mineral fertiliser for 24 years. The depth-dependent MP mass and number concentrations, plastic types, sizes and shapes were compared with the distribution of organic carbon and metals to provide insights into potentially transport-limiting factors. Polyethylene, polypropylene and polystyrene mass concentrations were screened down to 90 cm depth via pyrolysis-gas chromatography/mass spectrometry. MP number concentrations, additional plastic types, sizes, and shapes were analysed down to 40 cm depth using micro-Fourier transform-infrared imaging. Across all depths, MP numbers were twice and mass concentrations 8 times higher when sewage sludge was applied, with a higher share of textile-related plastics, more fibres and on average larger particles than in soil receiving mineral fertiliser. Transport of MPs beyond the plough layer (0-20 cm) is often assumed negligible, but substantial MP numbers (42 %) and mass (52 %) were detected down to 70 cm in sewage sludge-amended soils. The initial mobilization of MPs was shape- and sizedependent, because the fractions of fragmental-shaped and relatively small MPs increased directly below the plough layer, but not at greater depths. The sharp decline of total MP concentrations between 20 and 40 cm depth resembled that of metals and organic matter suggesting similar transport limitations. We hypothesize that the effect of soil management, such as ploughing, on soil compactness and subsequent transport by bioturbation and via macropores drives vertical MP distribution over long time scales. Risk assessment in soils should therefore account for considerable MP displacement to avoid underestimating soil exposure

Immobilizing arsenic in contaminated anoxic aquifer sediment using sulfidated and uncoated zero-valent iron (ZVI)

Arsenic (As) is carcinogenic and of major concern in groundwater. We collected sediment material from a contaminated anoxic aquifer in Sweden and investigated the immobilization of As by four commercial zero-valent iron (ZVI) particles. Solid-phase As and Fe speciation was assessed using X-ray absorption spectroscopy (XAS) and solution-phase As speciation using chromatographic separation. Without ZVI addition, arsenite dominated in solution and As(V) species in the solid phase. Adding ZVI caused a sharp increase in solution pH (9.3-9.8), favoring As oxidation despite a lowered redox potential. ZVI greatly improved As retention by complex binding of arsenate to the Fe(III) (hydr)oxides formed by ZVI corrosion. Uncoated ZVI, both in nano-and microscale, performed better than their sulfidated counterparts, partly due to occlusion of As by the Fe(III) (hydr) oxides formed. The effect of particle size (micro vs. nano ZVI) on As immobilization was small, likely because immobilization was related to the corrosion products formed, rather than the initial size of the particles. Our results provide a strong geochemical background for the application of ZVI particles to remove As in contaminated aquifers under anoxic conditions and illustrate that immobilization mechanisms can differ between ZVI in As spiked solutions and sediment suspensions.Environmental implication: Arsenic ranks first on the list by the US ATSDR of substances posing a threat to human health and the WHO considers groundwater the riskiest source for human intake of As. However, dealing with As contamination remains a scientific challenge. We studied the immobilization of groundwater As by commercially available ZVI particles at field-realistic conditions. Arsenic immobilization was highly efficient in most cases, and the results suggest this is a promising in situ strategy with long-term performance. Our results provide a strong geochemical background for using ZVI to remove As in contaminated anoxic aquifers

A critical evaluation of short columns for estimating the attachment efficiency of engineered nanomaterials in natural soils

Short, saturated packed columns are used frequently to estimate the attachment efficiency (alpha) of engineered nanomaterials (ENMs) in relatively homogeneous porous media, but a combined experimental and theoretical approach to obtain alpha-values for heterogeneous natural soils has not yet been agreed upon. Accurately determined alpha-values that can be used to study and predict ENM transport in natural soils should vary with ENM and soil properties, but not with experimental settings. We investigated the effect of experimental conditions, and used different methods to obtain soil parameters, essential to calculate alpha. We applied 150 different approaches to determine alpha-values from 52 transport experiments using short columns with 5 different natural soils and 20 and 80 nm gold- or 27 nm silver sulphide ENMs. The choice of column end-filter material and pore size appeared critical to avoid overestimating alpha owing to filter - ENM interactions and/or incomplete saturation of the column. Using a low ionic strength (4.4 x 10-5 mol L-1) artificial rain water as an aqueous medium avoided ENM homo- or heteroaggregation in all soils, as confirmed by single-particle inductively coupled plasma - time of flight mass spectrometry. ENM breakthrough curves could be modelled using colloid filtration theory assuming irreversible attachment only. alpha-Values calculated from this model, having the grain size represented by a single average size, accounting for dispersivity and effective porosity based on a prior inert tracer test, explained up to 42% of the variance in alpha as revealed by partial least squares analysis. However, column length and dispersivity remained as important experimental parameters, which calls for further standardisation efforts of column tests with ENMs in natural soils, preferably cross-validated with batch tests

Size dependence of silver nanoparticle removal in a wastewater treatment plant mesocosm measured by FAST single particle ICP-MS

The quantities of engineered nanoparticles (NP) released to the environment are often influenced by their fate in waste water treatment plants (WWTP). Here, 40 nm silver NP (AgNP) were spiked into a mesocosm simulating the process used at a major municipal WWTP. The evolution of the mass distributions and number concentrations were followed by fast acquisition speed technique single particle inductively coupled mass spectrometry (FAST spICP-MS) using a high-resolution ICP-MS. It was thus possible to detect smaller Ag containing NP than hitherto possible in similar studies. These small particles (ca. 5-10 nm in corresponding metallic Ag equivalent spherical diameter) were possibly dissolved Ag+ precipitated as Ag2S particles. They were detected immediately upon spiking and were stable with respect to aggregation and thus much less removed by the WWTP process compared to the 40 nm AgNP. The results also suggested that any transformation of the latter AgNP occurred without dissolution. Most of these larger AgNP were probably removed by aggregation with large floc particles and subsequent sedimentation with the suspended particulate matter in the simulated WWTP process. The results have implications for differentiating the fate of nanoparticles as a function of size and demonstrate how spICP-MS can reveal such size-dependent fate dynamics

Nanoplastic transport in soil via bioturbation by Lumbricus terrestris

Plastic pollution is increasingly perceived as an emerging threat to terrestrial environments, but the spatial and temporal dimension of plastic exposure in soils is poorly understood. Bioturbation displaces microplastics (>1 μm) in soils and likely also nanoplastics (<1 μm), but empirical evidence is lacking. We used a combination of methods that allowed us to not only quantify but to also understand the mechanisms of biologically driven transport of nanoplastics in microcosms with the deep-burrowing earthworm Lumbricus terrestris. We hypothesized that ingestion and subsurface excretion drives deep vertical transport of nanoplastics that subsequently accumulate in the drilosphere, i.e., burrow walls. Significant vertical transport of palladium-doped polystyrene nanoplastics (diameter 256 nm), traceable using elemental analysis, was observed and increased over 4 weeks. Nanoplastics were detected in depurated earthworms confirming their uptake without any detectable negative impact. Nanoplastics were indeed enriched in the drilosphere where cast material was visibly incorporated, and the reuse of initial burrows could be monitored via X-ray computed tomography. Moreover, the speed of nanoplastics transport to the deeper soil profile could not be explained with a local mixing model. Earthworms thus repeatedly ingested and excreted nanoplastics in the drilosphere calling for a more explicit inclusion of bioturbation in nanoplastic fate modeling under consideration of the dominant mechanism. Further investigation is required to quantify nanoplastic re-entrainment, such as during events of preferential flow in burrows

Oncogene advance online publication

The Raf-1 serine/threonine kinase is a key protein that is implicated in the transmission of many growth and cell survival signals. In the present study we demonstrate that apoptosis of hematopoietic cells induced by IL-3-deprivation is associated with the cleavage of Raf-1, resulting in the separation of the N-terminal regulatory domain and the C-terminal kinase domain. Raf-1 cleavage specifically occurs upon triggering of the mitochondrial death pathway, and coincides with the activation of specific caspases. Moreover, Bcl-2 overexpression or treatment with the caspase inhibitor z-VAD.fmk completely prevented Raf-1 cleavage, whereas caspase inhibition by treatment of cells with Ac-DEVD.fmk or z-IETD.fmk, or CrmA overexpression had no effect. Furthermore, in vitro cleavage studies indicate that caspase-9, which is the apical protease in the mitochondrial death pathway, is able to cleave Raf-1 at position D279. Cell fractionation studies showed that the Raf-1 C-terminal fragment that is generated upon IL-3 withdrawal is localized predominantly to the mitochondria. In addition, constitutive expression of this C-terminal Raf-1 fragment fused to a mitochondrial targeting sequence in Ba/F3 pre-B cells significantly delays apoptosis induced by IL-3 withdrawal. These results suggest an important role for caspase-9 mediated cleavage of Raf-1 in the negative feedback regulation of hematopoietic cell apoptosis induced by growth factor withdrawal

Short-Term Outcomes of Secondary Liver Surgery for Initially Unresectable Colorectal Liver Metastases following Modern Induction Systemic Therapy in the Dutch CAIRO5 Trial

Objective: To present short-term outcomes of liver surgery in patients with initially unresectable colorectal liver metastases (CRLM) downsized by chemotherapy plus targeted agents. Background: The increase of complex hepatic resections of CRLM, technical innovations pushing boundaries of respectability, and use of intensified induction systemic regimens warrant for safety data in a homogeneous multicenter prospective cohort. Methods: Patients with initially unresectable CRLM, who underwent complete resection after induction systemic regimens with doublet or triplet chemotherapy, both plus targeted therapy, were selected from the ongoing phase III CAIRO5 study (NCT02162563). Short-term outcomes and risk factors for severe postoperative morbidity (Clavien Dindo grade ≥ 3) were analyzed using logistic regression analysis. Results: A total of 173 patients underwent resection of CRLM after induction systemic therapy. The median number of metastases was 9 and 161 (93%) patients had bilobar disease. Thirty-six (20.8%) 2-stage resections and 88 (51%) major resections (>3 liver segments) were performed. Severe postoperative morbidity and 90-day mortality was 15.6% and 2.9%, respectively. After multivariable analysis, blood transfusion (odds ratio [OR] 2.9 [95% confidence interval (CI) 1.1-6.4], P = 0.03), major resection (OR 2.9 [95% CI 1.1-7.5], P = 0.03), and triplet chemotherapy (OR 2.6 [95% CI 1.1-7.5], P = 0.03) were independently correlated with severe postoperative complications. No association was found between number of cycles of systemic therapy and severe complications (r = -0.038, P = 0.31). Conclusion: In patients with initially unresectable CRLM undergoing modern induction systemic therapy and extensive liver surgery, severe postoperative morbidity and 90-day mortality were 15.6% and 2.7%, respectively. Triplet chemotherapy, blood transfusion, and major resections were associated with severe postoperative morbidity