The unusual suspects: Screening for persistent, mobile, and toxic plastic additives in plastic leachates.

Plastic additives are a diverse group of chemical compounds added to plastic products to give them their unique physical-chemical properties. Persistent, mobile, and toxic (PMT) plastic additives are a highly polar, environmentally stable sub-group of plastic additives with a variety of uses in plastic products. Due to their mobility into water, they can pose a significant long-term risk to the aquatic environment. Despite the potential threat, PMT plastic additives remain largely unregulated and under-studied. Notably, there is a need for dedicated analytical methodology and leaching studies to determine their potential emission from plastic products. Here we present an optimized leaching protocol and novel instrumental analysis method for the screening of 124 PMT plastic additives registered for use in Canada using high performance liquid chromatography with quantitative time-of-flight mass spectrometry (HPLC-QToF-MS). The analytical method covered a log Kow/Dow range between 0.21 and 6.02, which covered 72% of the PMT plastic additives used in Canada. A total of 52 PMT plastic additive suspects were leached in the optimization experiments, 44 of which were unique based on accurate mass and retention time. The conditions that resulted in the greatest numbers of PMT plastic additives leached were lake water, UV light exposure, and a timeframe of approximately 30 days. The analytical and leaching methods presented here offer new tools to study PMT plastic additives and assess their leaching in an environmentally relevant matrix, which can inform monitoring, threat assessment, and regulatory efforts moving forward.

Ancient Lowland Maya neighborhoods: Average Nearest Neighbor analysis and kernel density models, environments, and urban scale.

Many humans live in large, complex political centers, composed of multi-scalar communities including neighborhoods and districts. Both today and in the past, neighborhoods form a fundamental part of cities and are defined by their spatial, architectural, and material elements. Neighborhoods existed in ancient centers of various scales, and multiple methods have been employed to identify ancient neighborhoods in archaeological contexts. However, the use of different methods for neighborhood identification within the same spatiotemporal setting results in challenges for comparisons within and between ancient societies. Here, we focus on using a single method-combining Average Nearest Neighbor (ANN) and Kernel Density (KD) analyses of household groups-to identify potential neighborhoods based on clusters of households at 23 ancient centers across the Maya Lowlands. While a one-size-fits all model does not work for neighborhood identification everywhere, the ANN/KD method provides quantifiable data on the clustering of ancient households, which can be linked to environmental zones and urban scale. We found that centers in river valleys exhibited greater household clustering compared to centers in upland and escarpment environments. Settlement patterns on flat plains were more dispersed, with little discrete spatial clustering of households. Furthermore, we categorized the ancient Maya centers into discrete urban scales, finding that larger centers had greater variation in household spacing compared to medium-sized and smaller centers. Many larger political centers possess heterogeneity in household clustering between their civic-ceremonial cores, immediate hinterlands, and far peripheries. Smaller centers exhibit greater household clustering compared to larger ones. This paper quantitatively assesses household clustering among nearly two dozen centers across the Maya Lowlands, linking environment and urban scale to settlement patterns. The findings are applicable to ancient societies and modern cities alike; understanding how humans form multi-scalar social groupings, such as neighborhoods, is fundamental to human experience and social organization.

Persistent, mobile, and toxic plastic additives in Canada: properties and prioritization.

The hazards of many plastic additives on human and environmental health are well documented. However, little emphasis has been put on plastic additives that are persistent, mobile, and toxic (PMT) rather than persistent, bioaccumulative, and toxic. Due to their high mobility and stability, it is unlikely that wastewater treatment plants will effectively remove PMT plastic additives. Herein, an in silico analysis was performed to (1) assess the retention of PMT plastic additives registered for use in Canada in wastewater treatment plants; and (2) determine whether their physical-chemical properties and structural features can be used as identifiers for PMT plastic additives with particularly low retention. We identified 124 PMT plastic additives of which 52% had less than 20% removal from wastewater treatment based on predictions using the model SimpleTreat. Log Kaw, log Kow/Dow, and log Koc/Doc ranges were defined that are indicative of low retention PMT plastic additives. Furthermore, it was found that non-halogenated PMT plastic additives that contain nitrogen are most likely to be poorly retained in wastewater treatment plants. The results of this study provide screening and prioritization criteria, as well as a suspect list for PMT plastic additives.

A high-throughput platform for the rapid screening of vitamin D status by direct infusion-MS/MS.

Vitamin D is an important fat-soluble prohormone with pleiotropic effects on human health, such as immunomodulation of the innate and adaptive immune system. There is an unmet clinical need for a rapid screening platform for 25-hydroxyvitamin D (25OH-D) determination without chromatographic separation that offers better precision and accuracy than immunoassays. Here, we introduce a high-throughput method for assessing vitamin D status from blood specimens based on direct infusion-MS/MS (DI-MS/MS) following click derivatization using 2-nitrosopyridine. We developed an optimized liquid-phase extraction protocol to minimize ion suppression when directly infusing serum or plasma extracts via a capillary electrophoresis system for quantitative determination of 25OH-D. Acceptable reproducibility (mean coefficient of variation = 10.9%, n = 412), recovery (mean = 102% at 15, 30, and 45 nmol/l), and linearity (R2 > 0.998) were achieved for 25OH-D with lower detection limits (limit of detection ∼1.2 nmol/l, S/N ∼ 3), greater throughput (∼3 min/sample), and less bias than a commercial chemiluminescence immunoassay prone to batch effects. There was mutual agreement in 25OH-D concentrations from reference blood samples measured by DI-MS/MS as compared with LC-MS/MS (mean bias = 7.8%, n = 18). We also demonstrate that this method could reduce immunoassay misclassification of vitamin D deficiency in a cohort of critically ill children (n = 30). In conclusion, DI-MS/MS offers a viable alternative to LC-MS/MS for assessment of vitamin D status in support of large-scale studies in nutritional epidemiology as well as clinical trials to rapidly screen individual patients who may benefit from vitamin D supplementation.

Characterization of the interaction between tumor necrosis factor-stimulated gene-6 and heparin: implications for the inhibition of plasmin in extracellular matrix microenvironments.

TSG-6, the secreted product of tumor necrosis factor-stimulated gene-6, is not constitutively expressed but is up-regulated in various cell-types during inflammatory and inflammation-like processes. The mature protein is comprised largely of contiguous Link and CUB modules, the former binding several matrix components such as hyaluronan (HA) and aggrecan. Here we show that this domain can also associate with the glycosaminoglycan heparin/heparan sulfate. Docking predictions and site-directed mutagenesis demonstrate that this occurs at a site distinct from the HA binding surface and is likely to involve extensive electrostatic contacts. Despite these glycosaminoglycans binding to non-overlapping sites on the Link module, the interaction of heparin can inhibit subsequent binding to HA, and it is possible that this occurs via an allosteric mechanism. We also show that heparin can modify another property of the Link module, i.e. its potentiation of the anti-plasmin activity of inter-alpha-inhibitor (IalphaI). Experiments using the purified components of IalphaI indicate that TSG-6 only binds to the bikunin chain and that this is at a site on the Link module that overlaps the HA binding surface. The association of heparin with the Link module significantly increases the anti-plasmin activity of the TSG-6.IalphaI complex. Changes in plasmin activity have been observed previously at sites of TSG-6 expression, and the results presented here suggest that TSG-6 is likely to contribute to matrix remodeling, at least in part, through down-regulation of the protease network, especially in locations containing heparin/heparan sulfate proteoglycans. The differential effects of HA and heparin on TSG-6 function provide a mechanism for its regulation and functional partitioning in particular tissue microenvironments.