Profiles and species of Mn, Fe and trace metals in soils near a ferromanganese plant in Bagnolo Mella (Brescia, IT)

For the last forty-five years (from 1974 to present) ferroalloy production in Bagnolo Mella, Northern Italy, has generated particulate emissions enriched in potentially toxic metals and metalloids including arsenic (As), lead (Pb) and manganese (Mn). Of these, Mn is unique in that it has a significant background concentration and is seldom studied as a contaminant but is potentially a significant toxin derived from dusts regionally. Here we examine the distribution, redistribution, speciation and bioavailability of the Mn-contaminated top soils affected by atmospheric emissions adjacent to the ferroalloy plant. Four sites, variably located in the study area in terms of both distance and direction from the plant, were considered as representative of increasing levels of industrial influence. Soil profiles showed that metal concentrations (measured by X-ray fluorescence) varied considerably by location, i.e. higher in the sites closer to the plant and also at the surface level, although distributed throughout the top 15 cm, suggesting appreciable redistribution possibly due to soil mixing or infiltration. Most metal concentrations were correlated, except Mn which was independent and more variable across the sites than the other elements. Sequential chemical extractions indicated that Pb was primarily associated with Mn oxides, while As was most significantly associated with iron oxides. When Mn concentration significantly exceeded background levels, it was present in phases that were resistant to acid dissolution, very different from typical uncontaminated soils. X-ray Absorption Near Edge Spectroscopy (XANES) analyses suggested this recalcitrant Mn phase is likely a Mn-bearing spinel such as magnetite, that can be particularly toxic if ingested or inhaled. These first results highlight the legacy of ferroalloy production on surrounding soils, as well as the importance of Mn speciation for soil apportionment evaluation and human exposure estimation

Production and Composition of Pyrogenic Dissolved Organic Matter From a Logical Series of Laboratory-Generated Chars

Though pyrogenic carbon (pyC) has been assumed to be predominantly stable, degradation and transfers of pyC between various pools have been found to influence its cycling and longevity in the environment. Dissolution via leaching may be the main control on loss processes such as microbial or abiotic oxidation, mineral sorption, or export to aquatic systems. Yet, little is known about the controls on pyrogenic dissolved organic matter (pyDOM) generation or composition. Here, the yield and composition of pyDOM generated through batch leaching of a thermal series of oak and grass biochars, as well as several non-pyrogenic reference materials, was compared to that of their parent solids. Over 17 daily leaching cycles, biochars made from oak at 250–650◦C released decreasing amounts of C on both a weight (16.9–0.3%, respectively) and C yield basis (7.4–0.2% C, respectively). Aryl-C represented an estimated 32–82% of C in the parent solids (identified by 13C-NMR), but only 7–38% in the leachates (identified by 1H-NMR), though both increased with pyrolysis temperature. PyC, often operationally defined as condensed aromatic carbon (ConAC), was quantified using the benzenepolycarboxylic acid (BPCA) method. Tri- and tetra-carboxylated BPCAs were formed from non-pyrogenic reference materials, thus, only penta- and hexa-carboxylated BPCAs were used to derive a BPCA-C to ConAC conversion factor of 7.04. ConAC made up 24–57% of the pyrogenic solid C (excluding the 250◦C biochar), but only about 9–23% of their respective leachates’ DOC, though both proportions generally increased with pyrolysis temperature. Weighted BPCA compound distributions, or the BPCA Aromatic Condensation (BACon) Index, indicate that ConAC cluster size increased in pyrogenic solids but not in leachates. Additional evidence presented suggests that both aromatic cluster size and O-containing functional group contents in the pyrogenic solid control pyC solubility. Overall, pyDOM was found to be compositionally dissimilar from its parent chars and contained a complex mixture of organic compound groups. Thus, it is expected that estimates of dissolved pyC production and export, made only by detection of ConAC, are too low by factors of 4–11

Microbial Labilization and Diversification of Pyrogenic Dissolved Organic Matter

With the increased occurrence of wildfires around the world, interest in the chemistry of pyrogenic organic matter (pyOM) and its fate in the environment has increased. Upon leaching from soils by rain events, significant amounts of dissolved pyOM (pyDOM) enter the aquatic environment and interact with microbial communities that are essential for cycling organic matter within the different biogeochemical cycles. To evaluate the biodegradability of pyDOM, aqueous extracts of laboratory-produced biochars were incubated with soil microbes, and the molecular changes to the composition of pyDOM were probed using ultrahigh-resolution mass spectrometry (Fourier transform–ion cyclotron resonance–mass spectrometry). Given that solar irradiation significantly affects the composition of pyDOM during terrestrial-to-marine export, the effects of photochemistry were also evaluated in the context of pyDOM biodegradability. Ultrahigh-resolution mass spectrometry revealed that many different (both aromatic and aliphatic) compounds were biodegraded. New labile compounds were produced, 22 %–40 % of which were peptide-like. These results indicated that a portion of pyDOM has been labilized into microbial biomass during the incubations. Fluorescence excitation–emission matrix spectra revealed that some fraction of these new bio-produced molecules is associated with proteinaceous fluorophores. Two-dimensional 1H–1H total correlation nuclear magnetic resonance (NMR) spectroscopy identified a peptidoglycan-like backbone within the microbially produced compounds. These results are consistent with previous observations of peptidoglycans within the soil and ocean nitrogen cycles where remnants of biodegraded pyDOM are expected to be observed. Interestingly, the exact nature of the bio-produced organic matter was found to vary drastically among samples indicating that the microbial consortium used may produce different exudates based on the composition of the initial pyDOM. Another potential explanation for the vast diversity of molecules is that microbes only consume low molecular-weight compounds, but they also produce reactive oxygen species (ROS), which initiate oxidative and recombination reactions that degrade high molecular-weight compounds and produce new molecules. Some of the bio-produced molecules (212–308 molecular formulas) were identified in estuarine and marine (surface and abyssal oceanic), and 81–192 of these formulas were of molecular composition attributed to carboxyl-rich alicyclic molecules (CRAM). These results indicate that some of the pyDOM biodegradation products have an oceanic fate and can be sequestered into the deep ocean. The observed microbially mediated diversification of pyDOM suggests that pyDOM contributes to the observed large complexity of natural organic matter observed in riverine and oceanic systems. More broadly, our research shows that pyDOM can be substrate for microbial growth and be incorporated into environmental food webs within the global carbon and nitrogen cycles

Biolability of Fresh and Photodegraded Pyrogenic Dissolved Organic Matter From Laboratory-Prepared Chars

Pyrogenic dissolved organic matter (pyDOM) is known to be an important biogeochemical constituent of aquatic ecosystems and the carbon cycle. While recent studies have examined how pyDOM production, composition, and photolability varies with parent pyrogenic solid material type, we lack an understanding of potential microbial mineralization and transformation of pyDOM in the biogeosphere. Thus, leachates of oak, charred at 400 °C and 650 °C, as well as their photodegraded counterparts were incubated with a soil‐extracted microbial consortium over 96 days. During the incubation, significantly more carbon was biomineralized from the lower versus higher temperature char leachate (45% vs. 37% lost, respectively). Further, the photodegraded leachates were biomineralized to significantly greater extents than their fresh non‐photodegraded counterparts. Kinetic modeling identified the mineralizable pyDOC fractions to have half‐lives of 9–13 days. Proton nuclear magnetic resonance spectroscopy indicated that the majority of this loss could be attributed to low molecular weight constituents of pyDOM (i.e., simple alcohols and acids). Further, the quantification of benzenepolycarboxylic acid (BPCA) molecular markers indicated that condensed aromatic compounds in pyDOM were biomineralized to much lesser extents (4.4% and 10.1% decrease in yields of ΣBPCA‐C over 66 days from 400 °C and 650 °C oak pyDOM, respectively), but most of this loss could be attributed to the biomineralization of smaller condensed clusters (four aromatic rings or less). These results highlight the contrasting bioavailability of different portions of pyDOM, and the need to examine both to evaluate its role in soil or aquatic heterotrophy and its environmental fate in the hydrogeosphere

Biolability of Fresh and Photodegraded Pyrogenic Dissolved Organic Matter From Laboratory-Prepared Chars

Pyrogenic dissolved organic matter (pyDOM) is known to be an important biogeochemical constituent of aquatic ecosystems and the carbon cycle. While recent studies have examined how pyDOM production, composition, and photolability varies with parent pyrogenic solid material type, we lack an understanding of potential microbial mineralization and transformation of pyDOM in the biogeosphere. Thus, leachates of oak, charred at 400 °C and 650 °C, as well as their photodegraded counterparts were incubated with a soil‐extracted microbial consortium over 96 days. During the incubation, significantly more carbon was biomineralized from the lower versus higher temperature char leachate (45% vs. 37% lost, respectively). Further, the photodegraded leachates were biomineralized to significantly greater extents than their fresh non‐photodegraded counterparts. Kinetic modeling identified the mineralizable pyDOC fractions to have half‐lives of 9–13 days. Proton nuclear magnetic resonance spectroscopy indicated that the majority of this loss could be attributed to low molecular weight constituents of pyDOM (i.e., simple alcohols and acids). Further, the quantification of benzenepolycarboxylic acid (BPCA) molecular markers indicated that condensed aromatic compounds in pyDOM were biomineralized to much lesser extents (4.4% and 10.1% decrease in yields of ΣBPCA‐C over 66 days from 400 °C and 650 °C oak pyDOM, respectively), but most of this loss could be attributed to the biomineralization of smaller condensed clusters (four aromatic rings or less). These results highlight the contrasting bioavailability of different portions of pyDOM, and the need to examine both to evaluate its role in soil or aquatic heterotrophy and its environmental fate in the hydrogeosphere

Which exercise for low back pain? (WELBack trial) Predicting response to exercise treatments for patients with low back pain : a validation randomized controlled trial protocol

Introduction Exercise therapy is the most recommended treatment for chronic low back pain (LBP). Effect sizes for exercises are usually small to moderate and could be due to the heterogeneity of people presenting with LBP. Thus, if patients could be better matched to exercise based on individual factors, then the effects of treatment could be greater. A recently published study provided evidence of better outcomes when patients are matched to the appropriate exercise type. The study demonstrated that a 15-item questionnaire, the Lumbar Spine Instability Questionnaire (LSIQ), could identify patients who responded best to one of the two exercise approaches for LBP (motor control and graded activity). The primary aim of the current study isill be to evaluate whether preidentified baseline characteristics, including the LSIQ, can modify the response to two of the most common exercise therapies for non-specific LBP. Secondary aims include an economic evaluations with a cost-effectiveness analysis. Methods and analysis Participants (n=414) will be recruited by primary care professionals and randomised (1:1) to receive motor control exercises or graded activity. Participants will undergo 12 sessions of exercise therapy over an 8-week period. The primary outcome will be physical function at 2 months using the Oswestry Disability Index. Secondary outcomes will be pain intensity, function and quality of life measured at 2, 6 and 12 months. Potential effect modifiers will be the LSIQ, self-efficacy, coping strategies, kinesiophobia and measures of nociceptive pain and central sensitisation. We will construct linear mixed models with terms for participants (fixed), treatment group, predictor (potential effect modifier), treatment group×predictor (potential effect modifier), physiotherapists, treatment group×physiotherapists and baseline score for the dependent variable

Manganese concentrations in soil and settled dust in an area with historic ferroalloy production

Ferroalloy production can release a number of metals into the environment, of which manganese (Mn) is of major concern. Other elements include lead, iron, zinc, copper, chromium, and cadmium. Manganese exposure derived from settled dust and suspended aerosols can cause a variety of adverse neurological effects to chronically exposed individuals. To better estimate the current levels of exposure, this study quantified metal levels in dust collected inside homes (n=85), outside homes (n=81), in attics (n=6), and in surface soil (n=252) in an area with historic ferroalloy production. Metals contained in indoor and outdoor dust samples were quantified using inductively coupled plasma optical emission spectroscopy while attic and soil measurements were made with a XRF instrument. Mean Mn concentrations in soil (4600 μg/g) and indoor dust (870 μg/g) collected within 0.5 km of a plant exceeded levels previously found in suburban and urban areas, but did decrease outside 1.0 km to the upper end of background concentrations. Mn concentrations in attic dust were approximately 120 times larger than other indoor dust levels, consistent with historical emissions that yielded high airborne concentrations in the region. Considering the potential health effects that are associated with chronic manganese inhalation and ingestion exposure, remediation of soil near the plants and frequent, on-going hygiene indoors may decrease residential exposure and the likelihood of adverse health effects

Factors associated with access and adherence to artemisinin-based combination therapy (ACT) for children under five: a secondary analysis of a national survey in Sierra Leone.

BACKGROUND: Access and adherence to artemisinin-based combination therapy (ACT) are key challenges to effective malaria treatment. A secondary analysis of the Sierra Leone malaria Knowledge, Attitudes, and Practices (mKAP) survey was conducted to investigate access and adherence to ACT for the treatment of fever in children under-five. METHODS: The mKAP was a nationally representative, two-stage cluster-sample survey, conducted in 2012. Thirty primary sampling units per district were randomly selected using probability proportionate to size, based on national census estimates; 14 households were subsequently randomly selected and enrolled per sampling unit. The analysis was restricted to children under-five with fever in the past two weeks. Factors associated with access and adherence were assessed using multivariate logistic regression. RESULTS: Of 5169 enrolled households, 1456 reported at least one child under-five with fever in the past two weeks. Of the 1641 children from these households, 982 (59.8%) received any treatment for fever and were analysed for access to ACT; 469 (47.6%) received ACT and 466 were analysed for treatment adherence. Only 222 (47.4%) febrile children received ACT and completed 3-day treatment. In an adjusted analysis, factors associated with ACT access included knowledge of ACT (odds ratio [OR] 2.78, 95% CI 2.02-3.80; p < 0.001), knowledge of insecticide-treated nets (ITNs) (OR 1.84, 95% CI 1.29-2.63; p = 0.001), source of care (public health facility vs. other; OR 1.86, 95% CI 1.27-2.72, p = 0.001), geographic region (East vs. West; OR 2.30, 95% CI 1.20-4.44; p = 0.025), and age (24-59 vs. 0-23 months; OR 1.45, 95% CI 1.07-1.96; p = 0.016). The only factor associated with ACT adherence was time to treatment; children treated within 24 h were less likely to adhere (OR 0.55, 95% CI 0.34-0.89; p = 0.015). CONCLUSIONS: In 2012, access and adherence to ACT remained low in Sierra Leone. Knowledge of ACT and ITNs, and seeking care in the public sector, were most strongly associated with ACT access. National surveys provide important information on anti-malarial access and could be expanded to measure treatment adherence