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    Nocardiopsis changdeensis sp. nov., an endophytic actinomycete isolated from the roots of Eucommia ulmoides Oliv

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    Ocean warming and acidification affect the transitional C:N:P ratio and macromolecular accumulation in the harmful raphidophyte Heterosigma akashiwo

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    Joint use of location and acceleration data reveals influences on transitions among habitats in wintering birds

    Goose capture and trackingWe used rocket netting and leg snares to capture white-fronted geese in three regions in Texas (Rolling Plains, Lower Texas Coast, and South Texas Brushlands) and one region in Louisiana (Chenier Plain) from October to February 2016–2018 (Fig. 1). We determined age and sex of individuals by cloacal inversion, rectrices and other plumage characteristics27,28. We fit a solar powered GPS/ACC/Global System for Mobile communication (GSM) neckband tracking device (Cellular Tracking Technologies Versions BT3.0, BT3.5 and BT3.75; 44–54 g; Rio Grande, New Jersey, USA, and Ornitela OrniTrack-N38; 36 g; Vilnius, Lithuania), and an aluminum U.S. Geological Survey Bird Banding Laboratory metal leg band (Supplementary Fig. S1) on each bird. Geese were captured and tagged under USGS Bird Banding Permits #21314 and #23792, and Texas A&M University-Kingsville Institutional Animal Care and Use Committee #2015-09-01B. Captive geese were permitted under TAMUK IACUC #2018-01-11 and United States Fish and Wildlife Service Waterfowl Sale and Disposal permit #MB03808D-0. All applicable field methods were carried out in accordance with relevant guidelines and regulations. All animal handling protocols were approved by TAMUK IACUC committees and the USGS Bird Banding Laboratory. When multiple white-fronted geese were captured simultaneously, devices were only placed on adult females or adult males to eliminate the potential of placing devices on mated pairs, thus biasing independent data collection due to monogamous, long-term pair bonds in white-fronted geese. Location duty cycles were set to collect a GPS location every 30 min (i.e., 48/day) and location accuracy was 7.2 and 6.5 m for CTT and Ornitela devices, respectively. Data were uploaded once daily to respective online user interface websites when within areas of GSM coverage. When not in coverage areas, data were stored onboard the device until birds returned to coverage areas. All devices were equipped with a tri-axial ACC sensor which measured G-force (g; CTT devices) or millivolts (mV; Ornitela devices) at a fixed sampling scheme; CTT BT3.5 and Ornitela devices collected ACC data for a duration of 3 s every 6 min at 10 Hz, while BT3.0 devices collected data for a duration of 10 s every 6 min at 10 Hz. Generation BT3.0 devices were subsampled to match the sampling scheme of 3 s bursts before analyses. Ornitela units measured in mV were converted to G-force. We applied manufacturer- and tag-specific ACC calibration to all units, respectively, by collecting ACC data on each possible rotation for all axes when the device was stationary and applying the calibration to the raw ACC values (see Ref.29 for full calibration procedure). All devices recorded temperature in °C at each GPS fix. We censored GPS and ACC data from the time of release until individuals appeared to resume normal movement activity (i.e., roosting and foraging), as geese typically flew to the nearest wetland immediately after release where they remained without leaving while acclimating to wearing devices, which ranged from 1 to 7 days30. We defined the start of the winter period following a southward migratory movement from staging areas in Canada, without additional migratory movements southward below 40° 0′ 00″ N, or from the time of device deployment (minus device acclimation period) until geese made large northward migratory movements, or 28 February if geese remained in wintering areas.Figure 1Primary wintering regions of the Midcontinent population of greater white-fronted goose (Anser albifrons frontalis) in North America (excluding regions in Mexico). Transmitters were deployed during winters 2016–2018 in the Chenier Plain (Louisiana), Lower Texas Coast, and Rolling/High Plains regions. Geese that made winter movements outside of these defined regions were classified as ‘Other’ regions. Map created using Esri ArcMap (version 10.3.1; www.esri.com).Full size imageLand cover covariatesWe used publicly available spatial landcover data sets (30-m resolution) in combination with remote sensing to create landscape layers using programs Esri ArcMap (version 10.3.1), Erdas Imagine, and Program R (version 3.5.231). We used 2017 and 2018 National Agricultural Statistics Service Cropland Data Layer (CDL) data sets for agricultural crop types and freshwater wetlands, and the 2010 Coastal Change Analysis Program layer for saltwater and coastal wetland classifications29,32. Additionally, we used multi-spectral Landsat 8 Operational Land Imager satellite imagery, with principal component analysis on eight Landsat bands and a normalized difference vegetation index band, and unsupervised classification33,34 to accurately identify and create a spatial layer for peanut fields. We developed this layer for two regions with annual peanut agriculture (i.e., the Rolling/High Plains and South Texas Brushlands) using ground-truthed peanut fields, because the CDL layer did not identify this crop accurately based on our field observations during captures. We achieved  > 90% accuracy of peanut identification for each image independently based on annual ground-truthed observations of peanut fields. Finally, we grouped like-habitat categories to reduce the total number of categories to eight: corn, grass/winter wheat, herbaceous wetlands, other grains (i.e., soybeans, sorghum, and peanuts), rice, woody wetlands, open water/unconsolidated shore and other (Supplementary Table S1). White-fronted geese used several ecologically distinct regions in both winters of our study (Fig. 1), where the landscape composition of specific landcover types varied. To account for regional variability, we added region ID as a categorical variable to all GPS locations. Regions included the MAV, Chenier Plain, Texas Mid-coast, Lower Texas Coast, South Texas Brushlands, Texas Rolling/High Plains, and Other (i.e., locations outside of these identified wintering regions; Fig. 1). We used regional shapefiles of Gulf Coast Joint Venture Initiative Areas (Laguna Madre [Lower Texas Coast], Texas Mid-coast, and Chenier Plain35), and Level III Ecoregions (Mississippi Alluvial Valley, Texas Rolling/High Plains, and South Texas Brushlands36) as boundaries to classify data into regions. Due to insufficient and incompatible spatial layers for Mexico, we limited analyses to locations within the US.Location and acceleration data collectionRemotely determining behaviors of individuals using ACC data is most accurately addressed by developing a training dataset of known behaviors linked with ACC measurements of those behaviors18,37. To develop a training dataset, we collected video footage of two domestic white-fronted geese in Texas, US, and 18 tagged wild Greenland white-fronted geese (A. a. flavirostris) fitted with the same device types and the same data collection scheme, in Wexford, Ireland and Hvanneyri, Iceland during winters 2017–2018. We supplemented wild recordings with behavioral recordings of captive white-fronted geese as a proxy for wild individuals due to difficulty filming wild geese in inclement weather and obstructed video footage, which is common in ACC literature19,20,38,39. To replicate devices placed on wild white-fronted geese and account for potential variation in ACC measurements between device brands, among device versions and individual geese, we deployed three versions of devices used in this study on captive white-fronted geese during filming sessions38,40. We attached tracking devices to captive geese one week prior to video collection to allow geese to adjust to wearing devices. We collected ACC measurements for 3 s bursts, at 1 min intervals, at 10 Hz. We constructed a 149 m2 enclosure in an agricultural field to imitate an environment that wild geese may encounter. We created two enclosure settings allowing captive geese to forage on sprouted winter wheat (~ 2–15 cm) or on a randomly dispersed mixture of grain seeds (corn, wheat, sorghum) to account for both ‘grazing’ of vascular vegetation and ‘gleaning’ of agricultural grains to imitate foraging in wild geese. We used Sony Handycam DCR-SR45 video cameras, matched internal camera clocks with a running Universal Coordinated Time clock, and verbally re-calibrated the current time every 2 min during video footage collection. We filmed 119.5 h of video footage, and matched behavior with recorded ACC measurements by pairing video and device timestamps for each device using JWatcher41 and Program R.We characterized goose behaviors into four categories: ‘stationary’, ‘walk’, and ‘foraging’ from ground-truthed video footage, and ‘flight’ from visual inspection of the ACC data and consecutive GPS tracks during migration where device-measured speed remained  > 4.63 km/h (based on a natural break in the speed density distribution of all GPS locations). Each ACC burst was classified as only one behavior (i.e., a goose that was walking as it foraged was classified as ‘foraging’). We combined wild goose behaviors and captive goose behaviors after identifying minimal differences in ACC burst summary statistics29 for ‘stationary’ and ‘walk’ behaviors. We used ‘graze’ behaviors only from wild geese because of low sample size for captive geese and slight differences in ACC summary statistics between captive and wild geese for this behavior. ‘Glean’ foraging behavior was only classified from captive geese. We then combined ‘graze’ and ‘glean’ behaviors into an overall ‘foraging’ behavior to account for variation in foraging behavior of wild geese, and because machine learning models could not accurately distinguish between the two foraging modes40. We randomly subsampled all behaviors to 150 bursts if our dataset contained at least that many bursts to reduce the risk of artificially increasing prediction accuracy20. We determined there were insufficient differences in ACC signatures between CTT BT3.0 and BT3.5 versions by visual comparison of signatures and summary statistics, and merged all bursts into an overall CTT-specific training data set, and retained CTT- and Ornitela-specific training data sets to account for brand-specific ACC measurement schemes. The final training data sets consisted of 150 stationary, 150 walking, 118 foraging, and 150 flying bursts (CTT), and 150 stationary, 75 walking, 120 foraging, and 150 flying bursts (Ornitela).We used the training data sets to predict behaviors of tagged, wild white-fronted geese during winter with temporally aligned GPS and ACC data. We used a suite of supervised machine-learning algorithms and selected the algorithm with greatest prediction accuracy based on an 80% training, 20% testing sample approach. We tested random forest, support vector machines, K-nearest neighbors, classification and regression trees, and linear discriminant analysis, all with cross validation in Program R18,29,42. We evaluated models using three metrics defined in Ref.42: (1) overall classification accuracy as the percent of classifications in the test data set that were predicted correctly, (2) precision of assignment, the probability that an assigned behavior in the test data set was correct, and (3) model recall, the probability that a sample with a specific behavior in the test data set was correctly classified as that behavior by the model. Random forests provided the highest overall classification accuracy (95.6% for CTT and 96.0% for Ornitela), as well as high precision and recall for each behavior (CTT range 93.1–99.3, Ornitela range 88.9–100.0%), and therefore we labeled behaviors from wild goose ACC data using the random forests.Habitat transition modelOur habitat-transition model required temporally matched GPS and ACC datasets. Therefore, we subset all GPS locations to match the time-series of ACC data per individual because devices typically acquired GPS data longer than ACC data before device failure or individual mortality. For each GPS location, we extracted the landcover type and wintering region from spatial layers and retained temperature recorded from the device. To link classified ACC behaviors to GPS locations, we matched ACC timestamps between two GPS locations with the previous GPS timestamp. That is, all ACC bursts between two GPS locations were assigned backward to the previous GPS location. In this way, an individual’s first location is collected in GPS landcover type A, ACC data are collected in 5 bursts, their behaviors are classified and assigned to the first GPS location A and associated landcover type, followed by collection of GPS location B, in which the subsequent 5 ACC bursts are associated to GPS location/landcover type B. In the case of missing GPS locations, we matched ACC bursts to the previous GPS location only if the ACC timestamps were within 60 min of the GPS timestamp, and ACC bursts occurring greater than 60 min after GPS acquisition were removed until the next GPS fix. To account for temporal variation in habitat-behavior relationships, we calculated two continuous covariates representing time-of-day based on the local time associated with the timestamp of each GPS location for each individual. The variable cos(Diel) represented diurnal (negative values) and nocturnal (positive values) periods, and sin(Time) represented midnight until 11:59 a.m. (positive values) and noon until the following 11:59 p.m. (negative values), where high and low values ranged continuously between 1 and − 143. Our temporally matched time series of GPS and ACC data yielded 53,502 GPS locations linked with 300,348 ACC bursts across both winters.We used a Bayesian Markov model with Pólya-Gamma sampling following43), [cf. Refs.44,45] to determine how transitions between landcover types were influenced by behavior, temperature, time-of-day, and wintering region. The proportion of time spent foraging, walking, and stationary between each successive GPS fix was included as a covariate; flight was not included to reduce multicollinearity due to behavior proportions summing to one. Markov models account for non-independence among observations by assuming that the current state (i.e., landcover type) is dependent upon the previous state, and allow the determination of covariate influences on the probability of transitioning among states through a logistic link function. The transition probability from habitat i to habitat j at time t for individual n is modeled with multinomial logistic regression:$$begin{aligned} & logitleft( {p_{nijt} } right) = logleft( {frac{{p_{nijt} }}{{p_{niJt} }}} right) = mathop sum limits_{{r in {mathcal{R}}_{j} }} beta_{0jr} Ileft( {Region_{nt} = r} right) + beta_{1j} {text{cos}}left( {Diel_{nt} } right) \ & quad + beta_{2j} {text{sin}}left( {Time_{nt} } right) + beta_{3ij} Forage_{nt} + beta_{4ij} Walk_{nt} + beta_{5ij} Stationary_{nt} + beta_{6ij} Temperature_{nt} , \ end{aligned}$$where ({mathcal{R}}_{j}) is the set of wintering regions (r) where habitat (j) occurs, (Regio{n}_{rnt}) indicated wintering region (r), and (mathrm{cos}left({Diel}_{nt}right)) and (mathrm{sin}({Time}_{nt})) were temporal covariates (described above) for habitat j. Quantities ({Forage}_{nt}, {Walk}_{nt},mathrm{ and }{Stationary}_{nt}) were the scaled (mean = 0, standard deviation = 1) proportion of time spent in each behavior between transitions from habitat i to habitat j, and ({Temperature}_{nt}) was scaled ambient temperature (°C) for transitions from habitat i to habitat j. All coefficients for transitions to the baseline habitat (J) were set to 0 (i.e., ({beta }_{0Jr}) for all (r), ({beta }_{1J}), ({beta }_{2J}), ({beta }_{3iJ}), ({beta }_{4iJ}), ({beta }_{5iJ}),({beta }_{6iJ}), for all (i)). We set the baseline habitat (J) as open water/unconsolidated shore because this habitat is used primarily for both nocturnal roosting and diurnal loafing, included all behaviors, and transitions to all other landcover types were frequent in each region.The prior for the set of winter region intercepts for each habitat was:$${beta }_{0jr}sim N({beta }_{0j},{sigma }_{0jr}^{2}),$$for (rin {mathcal{R}}_{j}), ({beta }_{0j}) was the mean intercept, and ({sigma }_{0jr}^{2}) was set to 100. For ({beta }_{0j}), a vague prior mean 0 and σ2 = 100 was used with an assumed normal distribution.The Markov model was executed within a Bayesian framework to robustly quantify uncertainty. The Markov model assumed that data were collected at regular time intervals for both GPS (30 min) and ACC (6 min), however imperfect collection by devices created irregular data sets. Therefore, we subsampled GPS locations and constrained time series data to sequences where GPS locations missing  > 120 min intervals (i.e., 4 locations) were separated into sequences of regular time series data for each individual46. We extended43 by including a mix of both transition-specific effects (i.e., behaviors, temperature) and habitat-specific effects (i.e., wintering region, cos(Diel), and sin(Time)), where transition-specific effects were allowed to vary for a current habitat state, while habitat-specific effects were not. We included a mix of coefficients because initial model runs indicated that some effects were similar regardless of the current habitat (i.e., were habitat- and not transition-specific decisions). We also incorporated a model feature to exclude estimation of transitions that did not occur either within the dataset as a whole or within each specific wintering region because landcover types varied among them by setting those specific transition probabilities to zero. We centered and standardized all behavior and temperature covariates, sampled 50,000 iterations from the model posterior using one chain, and discarded the first 10,000 iterations as burn-in. We assessed model convergence by evaluating trace plots and setting random initial values, examined autocorrelation plots, and Geweke diagnostics using the R package ‘coda’47,48,49. More

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    Laboratory protocol is important to improve the correlation between target copies and metabarcoding read numbers of seed DNA in ground beetle regurgitates

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    Development of a treatment for water contaminated with Cr (VI) using cellulose xanthogenate from E. crassipes on a pilot scale

    Analysis of FTIRUnderstanding the functional groups involved in the biosorption of toxic metals is essential to elucidate the mechanism of this process. Groups such as carboxylic, hydroxyl and amine are among the main responsible for the absorption of metals by cellulose34 In the Fig. 1, show the FTIR of ECx.Figure 1FTIR of ECx before and after of adsorptions of Cr (VI).Full size imageAccording to13 the bandwidth at 3000–3600 cm−1 corresponds to bonds related to the -OH group. These hydrogen bonds are useful tools for cation exchange with heavy metals. This evidenced in the color spectrum (dark green) that represents an ECx sample with attached Cr (VI) after the adsorption process, where the stretching of the (OH) group lost part of its extension. The change observed in the peak from 3420 cm−1 of ECx to 3440 cm−1 in ECx-Cr indicates that these groups have a participation in the bond with the Cr (VI) ions. The variation of bands in the peak of the amines after adsorption confirms the participation of these groups in the adsorption process. This result confirmed by the ion exchange evaluation experiment discussed later in section SEM–EDX.The change in peak 3280, after Cr (VI) adsorption, indicates that EC removed Cr (VI) based on interaction with (OH), part of (OH) lost due to formation of vibrations of ascension O–Cr. Also, after Cr (VI) biosorption on ECx, the peak of the EC-S group is shifted to 590. This can be explained by surface complexation or ion exchange35.In general, comparable results reported in the literature for cellulose in the absorption of other toxic metals, as for other cellulose-derived biosorbentes in the removal of Cr (VI) ions36.One way to corroborate the information presented in the FTIR measurements is through SEM images since with these images it is possible to observe the distribution of the reagents in the ECx biomass treatment and subsequently the Cr (VI) adsorption process.SEM–EDXFigure 2 shows the micrographs obtained for the biomass before (a) the adsorption of Cr (VI), in addition to showing the distribution of the different biomass chemical modifications in (b) and in (c) it shows the distribution of chromium around all biomasses.Figure 2Biomass before (a) Cr (VI) adsorption, biomass chemical modifications in (b) and shows the distribution of chromium around the whole biomass (c).Full size imageFrom Fig. 2a, it can see that the biomass has a very irregular rough surface, with macropores and cracks. Many of these irregularities may associated with damage caused by the delignification process of E. crassipes cellulose with NaOH14. In Fig. 2b it is possible to visualize the components of the cellulose xanthogenate, coming from sodium, distributed throughout the biomass, a result like that reported in other studies35 The colored dots represent the elements in the samples, green dots represent carbon, red dots represent oxygen, and yellow dots represent the places where sodium lodged.Table 2 shows that, in addition to carbon and oxygen, the element with the greatest presence in the composition of pure waste is sodium and sulfur from the xanthogenate cellulose transformation process. Table 2 shows the physicochemical characterization of the ECx sample, through EDS.Table 2 Features of sample of ECx.Full size tableCellulose xanthogenate, is one of the cellulose transformations to improve the adsorption performance of heavy metals, this compound produced from dry and ground biomass, mixing with sodium hydroxide (NaOH) to remove lignin, creating alkaline biomass, then disulfide (CS2) added13,14. (CS2) reacts with hydratable hydroxycellulose, forming C-SNa complexes; these are responsible for the cation exchange with heavy metals. Metal ions enter the interior of E. crassipes with (CS2), exchanging with Na36,37.The SEM morphology of ECx and coupled with the high content of sulfides (7.3%) determined by the spectrum in Table 2, it further confirms that xanthate groups are successfully grafted onto the biomass of E. crassipes, and Fig. 3 represents this information based on13,36,37,38.Figure 3Prototype.Full size imageExchange biochemistry is usually identified as the main mechanism for the adsorption of metals in cellulose and its derivatives35 and through the evaluation of EDS this process could verify. Similar observations were made by36 where the adhesion of Cr (VI) in this biomass was observed. Also, in xanthogenate cellulose processes, the adhesion of Pb (II) to this type of biomass verified, concluding that this cellulose is important in the removal of heavy metals from water13.The SEM morphology of ECx with Cr (VI) coupled with the high content of sulfides determined by the spectrum in Table 3, was the determinate for the chemisorption’s of Cr (VI). The mechanism of Cr (VI) sorption by cellulose xanthate is:$$left[ {{4}left( {{text{C}}_{{6}} {text{H}}_{{{12}}} {text{O}}_{{6}} } right)} right]*{text{2CS}}_{{2}} {text{Na }} + {text{ Cr}}_{{2}} {text{O}}_{7}^{ – 2} to left{ {left[ {{4}left( {{text{C}}_{{6}} {text{H}}_{{5}} {text{O}}_{{6}} } right)} right] , *{text{2CS}}_{{2}} } right}*{mathbf{Cr}}_{{mathbf{2}}} + {text{Na}} + {text{7H}}_{{2}} {text{O}}$$where [4(C6H12O6)] *2CS2Na represents the xanthogenate biomass, and Cr2O7–2 represents the Cr (VI), that 4 parts of glucose xanthate react with the dichromate. In the Tables 3 and 4, the relationship between cellulose xanthogenate and Cr (VI), with related weights of 10.4 for Cr (VI).Table 3 Features of sample of ECx with Cr (VI).Full size tableTable 4 Researcher of process of the desorption.Full size tableMass balance in treatmentAdsorption is the phenomenon through which the removal of Cr (VI) achieved in the treatment systems; this quantified by means of the general balance equation of the treatment system as shown in Fig. 3.Adsorption is the phenomenon through which the removal of Cr (VI) achieved in treatment systems, this quantified by mass balance. Equation (1) shows the general balance of matter in the treatment system, together with the accumulation, inputs, and outputs of the system and the chemical process of adsorption.$${text{Acumulation }}upvarepsilon *frac{{partial {text{Cr}}left( {{text{VI}}} right)}}{{partial {text{t}}}} = {text{In}} frac{{partial {text{Cr}}left( {{text{VI}}} right)_{0} }}{{partial {text{t}}}} – {text{Out}}frac{{partial {text{Cr}}left( {{text{VI}}} right)}}{{partial {text{t}}}} – {text{Adsortion}},{rho b}frac{{partial {text{q}}}}{{partial {text{t}}}}$$
    (1)
    Accumulation represents by Eq. (1), where ∂C(VI) is the contaminant input to the treatment system, (ε) is the porosity of the bed, which calculated as the ratio between the density of the bed of treatment and the density of the microparticle of this biomass. This parameter must be above 0.548 achieved using particle diameters less than 0.212 mm, which favors contact between the contaminant and the particle49. The contaminant input to the treatment system represents by the design speed and the amount of contaminant that the system could treat. The output in the treatment system represents by the same input speed and the amount of contaminant that comes out. With these equations, the general material balance will be complete, summarized in Eq. (2), where it can see that the accumulation is equal to the input to the system, minus the output, and minus the adsorption.$$upvarepsilon *frac{{partial {text{Cr}}left( {{text{VI}}} right)}}{{partial {text{t}}}} = frac{{partial {text{Cr}} left( {{text{VI}}} right)}}{{partial {text{t}}}} – frac{{partial {text{Cr}} left( {{text{VI}}} right)}}{{partial {text{t}}}} – frac{{text{M}}}{{text{V}}}*frac{{partial {text{q}}}}{{partial {text{t}}}}$$
    (2)
    where V = System volume (ml), ε = Porosity, Co = Initial concentration of Cr (VI) (mg/ml), C = Final concentration Cr (VI) in the treated solution (mg/ml), Q = design flow (ml/min), Tb = Breaking time (Min), M = amount of biomass used (g), q = Adsorption capacity of the biomass used (mg/g).$${text{V}}*upvarepsilon *{text{Co}} = {text{Q}}*{text{Tb}}*{text{Co}} – {text{Q}}*{text{Tb}}*{text{C}} – {text{M}}*{text{q}}$$
    (3)
    Depending on the most important parameters when building a treatment system, Eq. (3) could use to model and validate the best form of treatment, for example, the necessary amount of biomass to use to treat a certain amount of contaminant, in the present investigation it used to establish the adsorption capacity in these initial treatment conditions. The remaining Eq. (4) determines the adsorption capacity.$${text{q}} = frac{{{text{QTbCo}}}}{{text{M}}} – frac{{{text{QTbCf}}}}{{text{M}}} – frac{{upvarepsilon {text{VCo}}}}{{text{M}}}$$
    (4)
    Adsorption capacity is generally taken through Eq. (5) for both batch and continuous experiments20,21But unlike Eqs. (5), (4) takes into account design variables such as flow rate (Q), rupture time (Tb), particle bed porosity ε, and vessel design volume (v).$${text{q}} = frac{{{text{v}}left( {{text{Co}} – {text{C}}} right)}}{{text{m }}}$$
    (5)
    where m: Mass used in the treatment, V: Volume, Co: Initial concentration, C: Final Concentration, Q: adsorption capacity.However, unlike Eqs. (5),  (4) considers the design variables such as flow rate (Q), rupture time (Tb), particle bed porosity ε and vessel design volume (v).When a desorption-elution process is involved for the reuse of biomass, Eq. (4) would be:$${text{q}}_{{text{T}}} = mathop sum limits_{j = 1}^{n} left[ {frac{{{text{QTbjCo}}}}{{text{M}}} – frac{{{text{QTbjCj}}}}{{text{M}}} – frac{{upvarepsilon {text{VCo}}}}{{text{M}}}} right]$$
    (6)
    where Q = design flow (ml/min), Tbj = Break time of use number j (Min), Co = Initial concentration of Cr (VI) (mg/ml), C = Final concentration Cr (VI) in the treated solution (mg/ml), V = System volume (ml), ε = Porosity, M = amount of biomass used (g), q_T = Total adsorption capacity of the biomass used (mg/g).This model (6) is design to determine the adsorption capacity when different elution processes have conducted, it will used to determine the new adsorption capacity and is one of the contributions of the present investigation.Result process of adsorptionsIn Fig. 4 shows the Cr (VI) adsorption process of the system.Figure 4Percentages of Cr (VI) removal the system for ECx.Full size imageVarious researchers have extensively studied the influence of factors such as bed height, flow rate and metal inlet concentration on rupture (Tb) curves. For example, the influence and similarity of the initial contaminant concentrations should be reflected as in the case of a tannery, with initial concentrations of 600 mg/l. Figure 4 shows the progress curves obtained for the study of Cr (VI) removal by the studied biomasses, reflecting the percentage of Cr (VI) removal in contrast to the treated volume, which is a very important parameter to time to scale the process.Regarding the effect of the input concentration, it can see in Fig. 5 that the breakpoint had a better performance in all the initial concentrations in the ECx biomass. comparing it with the EC-Na biomass (see Fig. 5), always obtaining breakpoints with more treated volume.Figure 5Percentages of Cr (VI) removal the system for EC-Na.Full size imageThe difference between the rupture curves between ECx and EC-Na indicates that the cellulose xanthate modification scheme should completed, although it can also elucidate that the EC-Na biomass has high yields compared to other biomass studied. for example, in Ref.34 investigate the biomass of E. crassipes without modifying, having removals below this alkaline cellulose.Adsorption capacitiesThrough Eq. (3), the adsorption capacity of ECx, using the initial concentration of 600 mg/l, since it was the maximum concentration used.The break point was around 1200 ml according to Fig. 6 and together with the flow rate of 15 ml/min; the break time obtained in 80 min.$${text{q}} = frac{{80{*}15{*}0.6}}{40} – frac{{80{*}15{*}0.04}}{40} – frac{{0.66{*}78{*}0.6}}{40}$$q: Adsorption capacity, Co: 0.6 mg/ml, C: 0.06 mg/ml, M: 40 g, Tb: rupture time 80 min, Q: 15 Flow rate ml/min, ε: 0.6649, V: Occupied volume: 70 ml.Figure 6Adsorption capacities in the different adsorption processes in the biomass ECx.Full size imageA result of 16 mg/g obtained in this continuous study for the biomass ECx. With this same equation it gives the capacity of the biomass EC-Na, with 11 mg/g.Desorption-Elution and reuseThrough Eq. (6), the sum of the Cr (VI) adsorption capacities established, after different biomass reuses due to EDTA elution. In the second treatment process, it yielded the following results under concentrations of 6 g/l of EDTA.$${text{q}}left( {text{T}} right) = frac{{60{*}15{*}0.6}}{40} – frac{{50{*}15{*}0.06}}{40} – frac{{0.66{*}68{*}0.6}}{40}$$Co: 0.6 mg/ml, C: 0.06 mg/ml, M: 45 g Biomass eluted with EDTA, Tb: rupture time: 60 min, Q: 15 Flow ml/min, ε: 0.6649, V: Occupied volume: 68 ml, q: 10 mg/g.Five Cr (VI) adsorption cycles performed using ECx and EC-Na cellulose in a continuous system to evaluate the regeneration and reuse potential. Between each biosorption cycle, a desorption cycle performed using three different concentrations of EDTA eluent.According to Figs. 6 and 7, although the adsorption capacity gradually decreases from the first adsorption process, it could consider that it is a satisfactory biomass recycling process and a design parameter for later stages of this treatment system.Figure 7Adsorption capacities in the different adsorption processes in the biomass EC-Na.Full size imageIn the experiments with concentrations of 6 g/l, five reuse processes obtained, obtaining a final sum of 52 mg/g. In concentrations of 3 g/l of EDTA, final capacities of 51 mg/g obtained lower than concentrations of 6 g/l but with half of this reagent. With concentrations of 1 g/l, final capacities of 33 mg/g obtained.The desorption processes of the EC-Na biomass with initial capacities of 11 mg/g were also evaluated and through desorption processes with EDTA of 3 g/l this biomass recycled on 5 occasions, reaching 32 mg/l in capacities of adsorption and like the EC-Na biomass, the ideal concentration in the process for desorption processes is 3 g/l, due to the considerable increase in reuse processes and low concentration compared to 6 g/l, which, although higher, does not this value is significant in the absorption capacity.Through Eq. (6) and with different bibliographic references, representative data obtained to feed this equation, determining the capacities of each of these biomasses together with the new capacities determining the desorption power of the different eluents shown and summarized in Table 4.For the EDTA eluent and with Eq. (6), satisfactory results evidenced by removing Al (II), reaching almost 150% of its adsorption capacity, corroborating what presented in the present investigation, also the EDTA reagent obtained interesting yields to recycle the cassava biomass increasing up to 40 mg/g. In Ref.39 used the biomass of Phanera vahlii to remove Cr (VI) obtaining results of 30 mg/g and with NaOH they reached capacities in the reuse process of this biomass up to 62 mg/g, reaching almost double of its total capacity41, also used NaOH for desorption processes with green synthesized nanocrystalline chlorapatite biomass, achieving results of 75% more. The eluent HCl is also a good chemical agent to use in desorption processes since it reached more than 100% in the reuse of biochar alginate for Cr (VI) but not so significant with biomass A. barbadensis Miller to remove Ni (II) and in40 significant results were also obtained to remove Pb (II) with pine cone Shell biomass. With the chemical agent HNO3, interesting contaminant recycling processes obtained, since more than 100% of the adsorption capacity of the biomasses used in this process used1,45.Mathematical models of adsorptionIn general, the models presented R2 greater than 0.95 for the adjustment of all the advance curves, which indicates a good adherence to the data, the model that best describes the behavior of the ECx system was the phenomenological model Thomas, which presented all the R2 values above 0.99.This model could use for the extension of the Cr (VI) ion biosorption system using cellulose xanthogenate, in the literature it is possible to observe that this model often tends to better adapt to the experimental data of the adsorption systems that use cellulose for the absorption of toxic metals28,30,31.With qt values remarkably close to the experimental values of Eq. (4) designed and presented in this investigation, indicating the validity of this equation where it reflects the maximum capacity obtained. Table 5 shows the adsorption constant of the Thomas model (Kt), which corresponds to the adsorption rate of Cr (VI) in the biomass49 This value was 0.048 (ml/mg*min) reflecting the speed with which Cr (VI) is chemisorbed in the biomass of ECx, in the EC-Na cellulose there was a Thomas model speed of 0.039 (ml/ mg*min) evidencing a lower adsorption rate than ECx. In the adsorption of Cr (VI) by rice biomass, the Thomas constant is 0.1 (ml/mg*min)47,50 also in the adsorption of Cr (VI) by biomass. Nanocrystalline chlorapatite biomass obtained at the Thomas constant 0.013 (ml/mg*min)49.Table 5 Summary of the experiments obtained with material ECx.Full size tableIn the Table 6, it presents summary of the experiments obtained with material EC-Na.Table 6 Summary of the experiments obtained with material EC-Na.Full size tableThe Cr (VI) adsorption process in the EC-Na biomass represented through the Bohart equation, since the sorption rate is proportional to the biomass capacity, obtaining an adsorption rate of 0.85(ml/mg*min). Having an alkalized biomass represents this model due to the homogeneity of this adsorbent.Mathematical models in desorption processesThe continuous desorption process with its fit to the Thomas model for biomass ECx always shows the fit of this model with significance, because this type of model fits representatively to desorption processes with good performance32,51 It can also verify that with values of qt it is close to the experimental values of Eq. (6) designed and presented in this research, indicating the validity of this equation again, where it reflects the maximum capacity obtained.In the Table 7. Show Summary of the experiments obtained with material ECx in process of desorption’s.Table 7 Summary of the experiments obtained with material ECx in process of desorption’s.Full size tableIn the Table 8 the EC-Na biomass had a different behavior and in its second and third cycle it adjusted to the Yoon model and later to the Bohart model.Table 8 Summary of the experiments obtained with material EC-Na in process of desorption’s.Full size tableThis behavior is due to the alkalinization of the biomass and this process makes the biomass a little more unstable. The values of qt, although a resemblance evidenced, were not so representative due to the little adjustment that there was with respect to the Thomas model. More

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    Fabrication of biochar derived from different types of feedstocks as an efficient adsorbent for soil heavy metal removal

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