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Models test our understanding of processes and can reach beyond the spatial and temporal scales of measurements. Multi-component Reactive Transport Models (RTMs), initially developed more than three decades ago, have been used extensively to explore the interactions of geothermal, hydrologic, geochemical, and geobiological processes in subsurface systems. Driven by extensive data sets now available from intensive measurement efforts, there is a pressing need to couple RTMs with other community models to explore non-linear interactions among the atmosphere, hydrosphere, biosphere, and geosphere. Here we briefly review the history of RTM development, summarize the current state of RTM approaches, and identify new research directions, opportunities, and infrastructure needs to broaden the use of RTMs. In particular, we envision the expanded use of RTMs in advancing process understanding in the Critical Zone, the veneer of the Earth that extends from the top of vegetation to the bottom of groundwater. We argue that, although parsimonious models are essential at larger scales, process-based models offer tools to explore the highly nonlinear coupling that characterizes natural systems. We present seven testable hypotheses that emphasize the unique capabilities of process-based RTMs for (1) elucidating chemical weathering and its physical and biogeochemical drivers; (2) understanding the interactions among roots, micro-organisms, carbon, water, and minerals in the rhizosphere; (3) assessing the effects of heterogeneity across spatial and temporal scales; and (4) integrating the vast quantity of novel data, including “omics” data (genomics, transcriptomics, proteomics, metabolomics), elemental concentration and speciation data, and isotope data into our understanding of complex earth surface systems. With strong support from data-driven sciences, we are now in an exciting era where integration of RTM framework into other community models will facilitate process understanding across disciplines and across scales.

Non-ionic surfactants are commonly used in parenteral protein formulations and include polysorbate 20, polysorbate 80 and poloxamer188. Recently, quantification and characterization of surfactants has generated considerable interest due to their connection to visible particle formation, a critical quality attribute for parenteral formulations. Typically, surfactant quantification is performed by mixed mode chromatography with evaporative light scattering detection (ELSD) or charged aerosol detection (CAD). However, these methods often suffer from loss of specificity in highly concentrated protein formulations. Here we present a mixed mode chromatography method using single quad mass detection, overcoming current limitations for highly concentrated proteins. In addition to content determination of intact surfactants, this method allows to quantify and characterize the predominant degradation patterns of polysorbates within a single measurement. Formulations with up to 200 mg/mL active pharmaceutical product (API) containing surfactant levels between 0.16 and 0.64 mg/mL were tested during method qualification. The obtained results for linearity (r > 0.99), precision (max. 3.8 % RSD) and accuracy (96-116 % recovery) meet current requirements for pharmaceutical products as defined in ICH Q2., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Geothermal and hydrothermal waters often contain high concentrations of dissolved sulfide, which reacts with oxygen (abiotically or biotically) to yield elemental sulfur and other sulfur species that may support microbial metabolism. The primary goal of this study was to elucidate predominant biogeochemical processes important in sulfur biogeochemistry by identifying predominant sulfur species and describing microbial community structure within high-temperature, hypoxic, sulfur sediments ranging in pH from 4.2 to 6.1. Detailed analysis of aqueous species and solid phases present in hypoxic sulfur sediments revealed unique habitats containing high concentrations of dissolved sulfide, thiosulfate, and arsenite, as well as rhombohedral and spherical elemental sulfur and/or sulfide phases such as orpiment, stibnite, and pyrite, as well as alunite and quartz. Results from 16S rRNA gene sequencing show that these sediments are dominated by Crenarchaeota of the orders Desulfurococcales and Thermoproteales. Numerous cultivated representatives of these lineages, as well as the Thermoproteales strain (WP30) isolated in this study, require complex sources of carbon and respire elemental sulfur. We describe a new archaeal isolate (strain WP30) belonging to the order Thermoproteales (phylum Crenarchaeota, 98% identity to Pyrobaculum/Thermoproteus spp. 16S rRNA genes), which was obtained from sulfur sediments using in situ geochemical composition to design cultivation medium. This isolate produces sulfide during growth, which further promotes the formation of sulfide phases including orpiment, stibnite, or pyrite, depending on solution conditions. Geochemical, molecular, and physiological data were integrated to suggest primary factors controlling microbial community structure and function in high-temperature sulfur sediments., (© 2012 Blackwell Publishing Ltd.)

Natural organic matter (NOM) can affect the behavior of arsenic within surface and subsurface environments. We used batch and column experiments to determine the effect of peat humic acids (PHA), groundwater fulvic acids (GFA), and a soil organic matter (SOM) extract on As sorption/transport in ferrihydrite-coated sand columns. A reactive transport model was used to quantitatively interpret the transport of As in flow-through column (breakthrough) experiments. We found that As(III) breakthrough was faster than As(V) by up to 18% (with OM) and 14% (without OM). The most rapid breakthrough occurred in systems containing SOM and GFA. Dialysis and ultrafiltration of samples from breakthrough experiments showed that in OM-containing systems, As was transported mostly as free (noncomplexed) dissolved As but also as ternary As-Fe-OM colloids and dissolved complexes. In OM-free systems, As was transported in colloidal form or as a free ion. During desorption, more As(III) desorbed (23-37%) than As(V) (10-16%), and SOM resulted in the highest and OM-free systems the lowest amount of desorption. Overall, our experiments reveal that (i) NOM can enhance transport/mobilization of As, (ii) different fractions of NOM are capable of As mobilization, and (iii) freshly extracted SOM (from a forest soil) had greater impact on As transport than purified GFA/PHA.