The toxicity and environmental persistence of anthropogenic per- and poly-fluoroalkyl substances (PFAS) are of global concern. To address legacy PFAS concerns in the United States, industry developed numerous replacement PFAS that commonly are treated as confidential information. To investigate the distribution of PFAS in New Jersey, soils collected from across the state were subjected to nontargeted mass-spectral analyses. Ten chloroperfluoropolyether carboxylates were tentatively identified, with at least three congeners in all samples. Nine congeners are ≥(CF2)7. Distinct chemical formulas and structures, as well as geographic distribution, suggest airborne transport from an industrial source. Lighter congeners dispersed more widely than heavier congeners, with the most widely dispersed detected in an in-stock New Hampshire sample. Additional data were used to develop a legacy-PFAS fingerprint for historical PFAS sources in New Jersey.
Understanding which compounds comprising the complex and dynamic marine dissolved organic matter (DOM) pool are important in supporting heterotrophic bacterial production remains a major challenge. We eliminated sources of labile phytoplankton products, advected terrestrial material and photodegradation products to coastal microbial communities by enclosing water samples in situ for 24 h in the dark. Bacterial genes for which expression decreased between the beginning and end of the incubation and chemical formulae that were depleted over this same time frame were used as indicators of bioavailable compounds, an approach that avoids augmenting or modifying the natural DOM pool. Transport- and metabolism-related genes whose relative expression decreased implicated osmolytes, carboxylic acids, fatty acids, sugars and organic sulfur compounds as candidate bioreactive molecules. FT-ICR MS analysis of depleted molecular formulae implicated functional groups ~ 30-40 Da in size cleaved from semi-polar components of DOM as bioreactive components. Both gene expression and FT-ICR MS analyses indicated higher lability of compounds with sulfur and nitrogen heteroatoms. Untargeted methodologies able to integrate biological and chemical perspectives can be effective strategies for characterizing the labile microbial metabolites participating in carbon flux.
Background Eutrophication of freshwater ecosystems resulting from nitrogen and phosphorus pollution is a major environmental stressor across the globe. In this systematic review, we compiled and synthesized literature on sestonic and benthic chlorophyll a (chl-a) responses to total nitrogen (TN) and total phosphorus (TP) concentrations in the water column in streams and rivers to provide a state-of-the-science summary of nutrient impacts on these endpoints. This review was motivated by the need for comprehensive information on stressor-response relationships for the most common nutrient and biotic response measures used by state-level environmental managers in the United States to assess eutrophication of lotic ecosystems and support environmental decision making. Methods Searches for peer-reviewed and non-peer-reviewed articles were conducted using bibliographic databases, specialist websites, and search engines. These returns were supplemented with citation mapping and requests for material from experts. Articles were screened for relevance using pre-determined eligibility criteria, and risk of bias was evaluated for each included article based on study type-specific criteria. Narrative summaries and meta-analysis were used to evaluate four primary stressor-response relationships: TN-benthic chl-a, TP-benthic chl-a, TN-sestonic chl-a, and TP-sestonic chl-a. Potential effects of modifying factors and study validity on review conclusions were assessed via sensitivity and sub-group analysis and meta-regression. Results Meta-analysis of 105 articles, representing 439 cause-effect pairs, showed that mean effect sizes of both benthic and sestonic chl-a responses to TN and TP were positive. Of the four stressor-response relationships examined, TP-sestonic chl-a had the most positive relationship, followed by TN-benthic chl-a, TN-sestonic chl-a, and TP-benthic chl-a. For individual U.S. states, mean effect sizes for the four stressor-response relationships were mostly positive, with a few exceptions. Chlorophyll measurement method had a moderately significant influence on mean effect size for TP-sestonic chl-a, with chl-a responding more strongly to TP if fluorometry versus spectrophotometry was used. Year of publication had a significant negative effect on mean effect size, as did mean nutrient concentration for both sestonic chl-a nutrient relationships. When the same study measured both TN and TP, chl-a tended to respond similarly to both nutrients. Sensitivity analysis indicated that conclusions are robust to studies with high risk of bias. Conclusions This systematic review confirms that nutrients consistently impact primary producer biomass in streams and rivers worldwide. It builds on previous literature syntheses evaluating chl-a responses to nutrient concentrations and confirms that benthic and sestonic chl-a respond positively to nutrients across a range of stream and river conditions, but also points to limits on these relationships (e.g., potential saturation at high nutrient concentrations). Lack of consistent reporting of contextual data limited our ability to examine how moderating factors influenced these stressor-response relationships. Overall, we provide nutrient managers responsible for protecting the quality of lotic ecosystems with a comprehensive evidence base for chl-a responses to TN and TP concentrations in the water column.
Physico-chemical characteristics of shugite rocks of Kazakhstan (Bakyrchik deposit) were studied using the methods of elementary analysis, IR-spectroscopy, scanning electron microscopy, Raman spectroscopy and X-ray phase analysis. The content of carbon in shungite rock was determined to be from 3% to 19%. The flotation technology for shungite rocks of Kazakhstan was developed, the content of carbon in the concentrate reaching 40.0%. When studying the elemental composition, the mineral part of shungite rocks was stated to be presented, mainly, by silicon, aluminium, calcium, magnesium, potassium, sodium, iron and titanium oxides. IR-spectroscopic investigations showed that in the concentrate, apart from polycyclic hydrocarbons containing methylene groups, there appeared carboxyl groups. The results of scanning electron microscopy (SEM) showed that flotation and thermal activation of shungite rocks on carbon allow obtaining a more developed surface structure and porosity. The structure of shungite carbon was shown by the method of Raman scattering to be close to that of glassy carbon. The results of X-ray diffraction analysis (XRD) of natural shungite rocks showed that the samples under study contained a carbonaceous substance and a number of mineral components: quartz, illite, bassanite, burgerite, muscovite. It is shown that shungite carbon of “Bakyrchik” deposit is identical to shungite of Zazhogino deposit in Russia. The stated physicochemical characteristics allow to determine the directions of the use of carbon concentrate for solution of ecological and technological problems.
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