It confirms that there was indeed a direct effect of hemp fabric on the Izod impact energy of the composites

Considering the average lengths before and after extrusion-injection molding , a reduction of about 2 times in the case of HF, 2.5 times for HF and 4 times for HF was observed. It follows that the reduction of fiber length was greater for longer initial fibers, similar to the results on simple PP/HF composites. Moreover, their length in the final composites was greater than for shorter initial fibers, which is consistent with previous results. For a deeper evaluation of fiber length reduction in PPM/HF composites after extrusion and injection molding, the length histograms of the initial fibers, collected after the mechanical treatment and before the incorporation in composites are given in Fig. 5. The representative images of the initial hemp fibers, HF, HF and HF are also shown in this figure. A thorough analysis of the initial fiber length shows that about 60% of HF are under 1mm in length, compared to 90% after processing, and only 27% in the case of HF and 4.5% in the case of HF, compared to 72% and 47% after processing. It follows that the proportion of “fines” is drastically increased in the case of longer fibers but it is maintained lower than 50% for HF. A side-by-side analysis of optical microscope images of HF before and after incorporation in composites highlights the intense defibrillation of the fibers. This is due to the concerted action of temperature and shear forces during processing in the double-screw extruder and injection molding machine. Average diameters of 91 ± 64, 99 ± 48 and 119 ± 69 m were obtained for the initial fibers, HF, HF and HF, after mechanical treatment. The lower dm value for HF and HF was caused by the more intensive mechanical treatment provided by the automatic cutting. The dm of HF decreased to 17.1 ± 11.1, 18.8 ± 9.8 and 23.8 ± 12.4 m after incorporation in PPM 30HF, PPM 30HF and PPM 30HF composites. Therefore, a rough calculation of the aspect ratio of the fibers,grow tent kit the length to diameter ratio, shows an increase from 12, 26 and 35 for mechanically treated HF,and to 33, 39 and 43 for HF in the composites containing these fibers.

Although both the length and the diameter of HF diminished after the melt processing of composites, the defibrillation seems more intense, which leads to an increase in the aspect ratio of the fibers. The analysis of fiber size after processing will be further used to understand the thermo-mechanical behavior of these composites.Natural fibers used as reinforcement of polymer matrices have been intensively investigated in recent decades and considered for diversified applications, from automotive, civil construction, sports, furniture, and packaging industries as well as in ballistic armors. The interest in the use of natural fibers ranges from their availability and renewability to intrinsic features, such as low density, biodegradability, cost-effectiveness, and low processing energy. In addition, the current need for replacing synthetic materials due to problems related to sustainability and non-renewable sources of energy led to a surging number of works to optimize their composite properties. Among the well-known natural fibers, the hemp fiber has historically been used in several applications such as textiles, manufacture of papers, and even in the pharmaceutical industry. Archaeologically, hemp is the oldest discovered natural fiber. The Columbia History of the World stated that the most antique relics of human industry are bits of hemp fabric discovered in tombs dating back to approximately 8000 BC. Nowadays, the plant Cannabis sativa, from which the industrial hemp fibers are extracted, is again widely grown in China, Europe, and Central Asia, after years of restriction in some countries. In fact, the C. sativa species produces less than 0.2 wt% of tetrahydrocannabinol , the, which is too low for use as a recreational drug, as in the case of marijuana, a popular denomination of Cannabis indica. The C. sativa fibers, responsible for keeping the trees upright, have its structural properties studied for reinforcement composites due to their remarkable strength and stiffness. Some historical applications corroborate its potential, such as when Henry Ford tried to adopt hemp-polymers composites in the automotive industry in 1941. Another example was the constructive details of the window frames and floor coverings, made of hemp fiber reinforced polymer composites used in facilities during the 2008 Beijing Olympics. Indeed, due to a relatively larger amount of cellulose and hemicellulose and lower microfibrillar angle,which are related to mechanical properties, the hemp fiber displays a remarkable tensile strength , elastic modulus and total strain. As such, after sisal, hemp is the world’s most applied natural fiber as reinforcement in composites.

However, a recognized disadvantage is the aforementioned variability in their properties, which is inherent to natural fibers in general and requires that each lot of fiber, obtained from a given supplier, to be preliminarily tested. This procedure will be carried out in the present work regarding basic mechanical and thermal properties. According to Shahzad, the main hemp fiber reinforced composite matrices are polypropylene and unsaturated polyester due to easy processing and cost. On the other hand, with comparable properties and cost of UP, epoxy is another thermoset polymer that has not been often used as a composite matrix for hemp fibers. As shown in our literature survey in Fig. 1, there is an emerging tendency to study epoxy composites reinforced with hemp fiber. In this decade an approximately exponential rise is occurring in the related number of articles. According to Fig. 1, today seven new publications already have a DOI number. In particular, flexural strength and modulus of 30 vol% of hemp fiber epoxy composites were found to surpass the corresponding flexural strength and modulus of polyester composites with an equal amount of same hemp fibers. In spite of the raising interest, Fig. 1, for epoxy composites reinforced with hemp fiber, no work has so far specifically investigated epoxy composites with hemp fabric. A surging area, where natural fiber/fabric reinforced polymer composites are attracting increasing attention, is that of personal ballistic protection. In addition to the numerous works cited in the aforementioned review papers, several recent publications reported on the ballistic protection provided by NFCs. As part of multilayered armor system , these NFCs display ballistic performance superior to commonly applied Kevlar and Dyneema laminates. Although much weaker than synthetic aramid and ultra-high molecular weight polyethylene, natural fibers possess the same capacity of absorbing the ballistic energy by capturing the fragments after the bullet impact against the MAS front ceramic. In view of these disclosed NFCs superior ballistic performance combined with lower density, cost effectiveness and sustainability, one might expect that hemp fabric reinforced epoxy composite could be used for ballistic protection. In a pioneer works, Wambua et al. investigated the response of 46 vol% of hemp fabric reinforced PP composite to ballistic impact by 1.1 g fragment simulating projectile . Their main result revealed an absorbed kinetic energy of 36 J associated with a limit ballistic impact velocity of 260 m/s.

Therefore, the primary objective of the present work was to investigate for the first time the ballistic performance of epoxy composites reinforced with up to 30 vol% of hemp fabric against 0.22 ammunition. As a preliminary investigation, the mechanical and thermal properties of the aforementioned composites are also investigated to characterize the specific reinforcement effect of our Brazilian supplied hemp fabric. The possible variability of results was statistically evaluated using the analysis of variance and the Tukey test.Table 1 shows the results for all conditions: composites reinforced with 10, 20, and 30 vol% of hemp fabric and neat epoxy, which was used as a control group. For better visualization, the average values were plotted in Fig. 4. All tested specimens were completely fractured, validating the results obtained as required by the standard. The graph in Fig. 4 presents a continuous increase in the impact energy along with the fabric volume fraction and a lower standard deviation for the plain epoxy resin compared to the composites due to the non-uniform proprieties of natural fiber. This behavior was observed in previous works for different composites and is expected as the amount of reinforcement is related to the increase of energy necessary to break the samples. Comparatively, the 30 vol% hemp fabric-epoxy composite presented only about 36% lower absorbed energy than the 30 vol% curaua-polyester composite, which, in another work, was presented as an acceptable ballistic performance. Fig. 5 shows the broken specimens after the Izod impact test. By visual analysis, the fracture surface of specimens with 0 and 10 vol%, and , respectively, reveal a smoother surface related to a brittle fracture tendency. On the other hand, the fracture surface of the samples reinforced with 20 and 30 vol% hemp fabric,indoor grow tent and gets more irregular as the volume fraction of reinforcement increases, which could indicate a brittleeductile transition. From the results, in Table 1 and Fig. 4, Table 2 presents the ANOVA analysis for the impact energy absorbed. The equality hypothesis with a confidence level of 95% was rejected, as F was higher than the Fc.The Tukey test honest significant difference for the absorbed impact of the plain epoxy result and the composite values above this result present a significant difference. Hence, the results in Table 3 show that the impact strength of the 30 vol% hemp fabric composites is the best amid the tested composites. It is important to note that the values are always greater than the HDS calculated, which suggests that the incorporation of hemp fabric provides an effective reinforcement to the epoxy resins for all volume fractions.

This points toward what was already presented in early works, in which the reinforcement contributed to a greater rupture surface area by interrupting or deviating the crack’s propagation.Table 4 presents the average results for the tensile strength of the hemp fabric-reinforced composites. From these values and the strain of the samples, it was also possible to calculate the elastic modulus. These results are plotted in Fig. 6 and , which correspond to tensile strength and elastic modulus, respectively, for better visualization. Table 4 also shows literature values for the tensile strength of the same neat epoxy resin. The results in Table 4 and Fig. 6 display relatively poor tensile properties for the 10 and 20 vol% hemp fabric reinforced composites comparatively with the neat epoxy resin. It suggests that these two fractions of fabric do not act as reinforcement when tensile loads are applied to the material. Consequently, the epoxy matrix bears most of the load applied during the test. As such, the hemp fabric incorporation has a negative effect on the composites and acts more as flaws in the material’s structure. However, the composites with 30 vol% hemp fabric improved considerably the tensile strength compared to the neat epoxy resin, which means that this amount of hemp fabric acts as an effective reinforcement for the material due to the mechanisms of restrict rupture of the fibers in the fabric that impart the tensile strength. This good performance, compared to other composites reinforced with hemp fibers, is an important parameter for the ballistic performance of the composites, as the tensile strength is associated with the penetration resistance of the target material. Also, it is possible to observe a considerable improvement of the elastic modulus for the composites reinforced with 30 vol% hemp fabric, which could be related to the higher stiffness of the hemp fiber. Although, the 10 and 20 vol% hemp fabric show lower values with a slight decrease attributed to a nonuniformity of the reinforcement’s properties. To better understand the behavior of the analyzed composites under tensile stress, Fig. 7 presents SEM images of the broken specimens, in which it can be noted different fracture mechanisms. The “river marks” present on the composites reinforced with 10 and 20 vol% hemp fabric, shown in Fig. 7 and , reveal low effectiveness of reinforcement of these composites due to limited fabric content and causes a brittle fracture for the material as the epoxy matrix bears most of the load.

Absolute and normalized organ weights were determined on selected tissues

Sixty male rats weighing 224-286 g and 60 female rats weighing 170-218 g were distributed to treatment groups stratified by body weight among the dose and control groups . For both the 14-day and the 90-day studies, body weights were recorded twice during the acclimation period and weekly for the duration of the study. Feed intake was determined at the same day body weights were determined. Filtered potable water and feed were provided ad libitum. Feed and water were assayed for detrimental substances and none were found at levels that would alter study results. In the 90-day study, sentinel rats were kept in the animal rooms. Serology done on samples collected at the end of the study from the sentinel rats were negative for Rat Parvovirus, Toolan’s Virus , Kilham Rat Virus, Rat Minute Virus, Parvovirus NS-1, Rat Coronavirus, Rat Theilovirus, and Pneumocystis carinii. The animals in the 14-day and the 90-day study were observed daily for clinical evidence of ill health and given physical exams weekly corresponding to body weight determinations. The physical exam included observing for changes in skin, fur, eyes, and mucous membranes, occurrence of secretions and excretions and autonomic activity . The exam also included changes in gait, posture, and response to handling, as well as the presence of clonic or tonic movements, stereotypies , or bizarre behavior . All abnormal observations were recorded. Rats in the 90-day study received a Functional Observation Battery in an open field for excitability, autonomic function, gait and sensorimotor coordination , reactivity and sensitivity and other abnormal clinical signs including, but not limited to convulsions, tremors, unusual or bizarre behavior, emaciation, dehydration and general appearance. Additionally, during week 12 rats in the 90-day study underwent a Motor Activity Assessment using a Photobeam Activity System [San Diego Instruments, Inc ] following recommended procedures. Investigators doing the physical examinations, Functional Observation Battery, and Motor Activity Assessment were blind to the treatments the rats were receiving. The clinical chemistry parameters for the 14-day and 90-studies are given in Table 5.

For the 14-day study, blood,vertical grow after overnight fasting, was collected before necropsy from the inferior vena cava while the rats were anesthetized with isoflurane. For the 90-day study, blood was collected from all groups for hematology and clinical chemistry on study day 94 for males and study day 95 for females in Groups 1 to 4 and on study day 124 for Groups 5 to 8 . Blood samples for hematology and clinical chemistry were collected by sublingual bleeding after the rats were anesthetized with isoflurane. Approximately 500 μL of blood was collected for hematologic parameters in a pre-calibrated tube containing Potassium EDTA4 anticoagulant and 1000 μL of whole blood was collected in tubes for clinical chemistry parameters . Whole blood samples were kept cold until examined in the laboratory using standard hematology methods. For clinical chemistry, blood was allowed to coagulate, and the samples were centrifuged in a refrigerated centrifuge. The serum supernatant was harvested and placed in cryotubes, and frozen and stored at -80 ◦C until thawed and assayed. Hematology parameters were determined on an ADVIA 120 Hematology System and clinical chemistry parameters were determined on a COBAS C311 autoanalyzer . Blood samples used to determine the prothrombin time and activated partial thromboplastin time were collected immediately before terminal sacrifice by venipuncture of the inferior vena cava during anesthesia with isoflurane. Approximately 1.8 mL of blood was collected in a pre-calibrated tube containing anticoagulant . These samples were centrifuged in a refrigerated centrifuge and the plasma was transferred to labeled tubes. Plasma samples were frozen and stored in a -80 ◦C freezer until thawed and analyzed on a Sysmex CA620 . The day before collection of samples for the clinical chemistry evaluations, the animals were placed in metabolism cages. Food was withheld for at least 15 hours prior to blood collection, and voided urine was collected from each animal. Urine samples were refrigerated until analyzed . Urine volume was measured, the appearance was recorded, chemical parameters were measured by Multistix® 10 SG Reagent Strips and urine sediment was evaluated by light microscopy. A full necropsy was done on each study animal including animals removed from the studies. Included in the necropsy were examination of the external body surface, body orifices, and the thoracic, abdominal and cranial cavities inclusive of contents. All surviving animals were weighed, anesthetized with isoflurane and exsanguinated from the abdominal aorta. All gross lesions were recorded.The eyes, epididymides, optic nerve and testes were fixed in modified Davidson’s fixative and then stored in ethanol.

All other tissues were fixed in 10% neutral buffered formalin. Specified tissues were embedded in wax, thin sections cut and stained with hematoxylin and eosin, and examined by light microscopy for histopathology . For the 14-day study, liver and adrenal glands from all treatment and control animals, and the kidneys from Groups 1 and 4 were examined by histopathology. For the 90-day study, tissues from all animals removed from the study, tissues from Groups 1 and 4 and the livers from Groups 2 and 3 and groups 5 to 8 were examined for histopathologic changes by light microscopy . All gross lesions observed were described, the tissues taken and examined by histopathology. All pathology procedures were under the supervision of aveterinary pathologist5 . Mean and standard deviations were calculated for all quantitative data. For all in-life endpoints that were identified as multiple measurements of continuous data over time , treatment and control groups were compared using a two-way analysis of variance , testing the effects of both time and treatment, with methods accounting for repeated measures in one independent variable. Significant interactions observed between treatment and time, as well as main effects, were further analyzed by a post hoc multiple comparisons test; e.g. Dunnett’s test of the individual treated groups to control. When warranted by sufficient group sizes, all endpoints with single measurements of continuous data within groups were evaluated for homogeneity of variances and normality. Where homogeneous variances and normal distribution was observed, treated and control groups were compared using a one-way ANOVA. When one-way ANOVA was significant, a comparison of the treated groups to control was performed with a multiple comparisons test, e.g., Dunnett’s test . Where variance was considered significantly different, groups were compared using a nonparametric method, e.g., Kruskal-Wallis non-parametric analysis of variance. When non-parametric analysis of variance was significant, a comparison of treated groups to control was performed, e.g., Dunn’s test. Significance was a probability value of p < 0.05. For hematology and clinical chemistry, the data from male and female rats were analyzed separately. Means and standard deviations were calculated for all quantitative clinical pathology parameters using Pristima® version 7 . These data were analyzed in a sequential manner. First, Bartlett’s test for homogeneity and Shapiro-Wilk test for normality was done.

If the Bartlett’s test for homogeneity and Shapiro-Wilk test for normality were not significant, a one-way analysis of variance followed with Dunnett’s test was performed. If the Bartlett’s test for homogeneity and Shapiro-Wilk test for normality were significant then data transformations to achieve normality and variance homogeneity were done. The order of transformations attempted was log, square root, and rankorder. If the log and square root transformations fail, the rank-order was used. When an individual observation was recorded as being less than a certain value, e.g., below the lower limit of quantitation, calculations were performed on one-half of the recorded value. For example, if bilirubin was reported as <0.1 or ≤0.1, then 0.05 was used for all calculations performed with that bilirubin data. When an individual observation was recorded as being greater than a certain value, e.g., above the upper limit of quantitation, then a greater value was used in place of the recorded value. For example, if specific gravity was reported as >1.100 or ≥1.100, then 1.100 was used for all calculation performed using that specific gravity value. For all statistical testing, significance was a probability value of p < 0.05. The mutagenicity potential of the test article as well as undiluted extracts were evaluated in the Bacterial Reverse Mutation Assay in accordance with FDA GLP and US FDA Redbook 2000 and ICH guidelines. Four strains of Salmonella typhimurium and one strain of Escherichia coli were used. The studies were conducted in the presence and absence of a metabolic activation system from male Sprague-Dawley rats which had been induced with phenobarbital and benzoflavone . The overlay agar and minimal glucose agar plates were purchased . The fresh bacterial suspension cultures in the nutrient broth were prepared so that they were in the late exponential phase of growth when used. The test article in olive oil was formulated as a solution in dimethyl sulfoxide to provide the required dose levels of up to 76,335 μg/plate to account for the 6.55% of active ingredient . For the undiluted extract prepared by isopropanol or supercritical CO2 extraction, indoor growers the extract was formulated as a solution in DMSO to provide the required dose levels up to 5000 μg/plate. Positive controls were used, both in the presence and absence of a metabolic activation system. The positive control substances included were sodium azide, ICR 191, daunomycin and methyl methanesulfonate for S. typhimurium strains TA100 and TA1535, TA1537, TA98 and E. coli WP2 uvrA, respectively in the absence of metabolic activation and 2-aminoanthracene for all strains in the presence of metabolic activation. The initial test for all test articles utilized the plate incorporation method in which the following materials were mixed and poured onto the minimal agar plate; 100 μL of the prepared test substance solutions/negative control/positive control substance, 500 μL of S9 mix or substation buffer, 100 μL bacterial suspension or 2000 μL overlay agar.

The plates were then incubated at 37 ◦C until the growth was adequate for enumeration. A confirmatory test for all test articles was conducted utilizing the pre-incubation method. The test or control substances, bacterial suspensions and the S9 mix or substitution buffer were incubated under agitation for approximately 30 minutes at 37 ◦C prior to mixing with the overlay agar and pouring onto the minimal agar plates and proceeding as for the initial test. The strains used and dose levels were the same as that in the initial test for all test articles. The plates for both tests were prepared in triplicate for each experimental point. For the undiluted isopropanol extract, the final doses utilized for both the initial and confirmatory tests were 1.58, 5.0, 15.8, 50, 158, 500, 1580 and 5000 μg/plate. For the undiluted supercritical CO2 extract, the final doses utilized were 1.58, 5.0, 15.8, 50, 158, 500, 1580 and 5000 μg/plate for the initial test and 0.5, 2.5 and 25 μg/plate for the confirmatory test. Due to toxicity noted for strains TA100 and TA1537 with the supercritical CO2 extract, a supplemental test was conducted to ensure five concentrations could be assessed without toxicity. Both the plate incorporation and pre-incubation methods were used as previously described at final doses of 0.5, 2.5 and 25 μg/plate. Following incubation, the number of colonies per plate was counted manually and/or with the aid of a plate counter. The mean and standard deviation were calculated for each set of triplicate plates. The test was considered valid if the control plates had normal background lawn; the mean revertant colony counts for each strain treated with vehicle was close to or within the expected laboratory historical control range or published values; and the positive controls should produce substantial increases in revertant colony numbers with the appropriate bacterial strain. The plates were also evaluated for cytotoxicity which is indicated by the partial or complete absence of a background lawn on non-revertant bacteria or a substantial dose-related reduction in revertant bacteria. Recently, there has been an increasing interest regarding the health benefits of CBD and other phytocannabinoids and with this increased interest, more research is also being conducted to assess the safety of these compounds for human consumption. The current studies were performed to better understand the toxicological profile of a CBD rich proprietary hemp extract and to assess the results in tandem with information currently available regarding the toxicity and safety of CBD. Marx et al. reports on a battery of GLP compliant toxicological studies which were conducted on a supercritical CO2 extract of the aerial parts of the C. sativa plant.

The values of initial adsorption rate and desorption constant varied in function of the copper concentration

Values of ki and correlation coefficients are listed in Table 3,from which it can be seen that the kinetics of copper adsorption on the SHI-W and SHI-C samples followed this model with R2 values higher than 0.95,indicating that intraparticle diffusion was involved in the adsorption process.For these samples,it seems that physisorption played the main role in the adsorption mechanism.However,for the SHI-BTCA,the R2 values did not support the fact that the metal-adsorption data closely follow this model,suggesting that,in this case,the diffusion mechanism is not the main interaction,and the process was mainly controlled by chemisorption.Nevertheless,for the three selected materials and the entire concentration range studied ,it was noted that the adsorption process tends to be followed by two linear regions with non-zero intercepts: the initial curved portion of the plots indicated a boundary layer effect while the second linear portion is due to intraparticle diffusion.Indeed,the data did not pass through the origin,indicating that intraparticle diffusion was not the only rate-limiting mechanism and that some other interactions also played an important role.The calculated ki values for each initial concentration indicated that,when the metal concentration was augmented,the rate constant increased for all the tested samples.The values of C also increased with copper concentration.However,the analysis of the data indicated that deviations from Weber and Morris model mainly occurred at high initial metal concentrations.Similar interpretations on this were reported before.The Elovich model,inspired by Zeldowitsch’s model and developed for gaseous systems,helps to predict the mass and surface diffusion,activation and deactivation energy of a given system,pot drying determining the nature of adsorption on the heterogeneous surface of the adsorbent,whether chemisorption or not.

This model is expressed by Eq.where a and b are the initial rate and desorption constant,respectively,during any experiment.Fig.6 shows that,for the three selected samples,the metal adsorption also fitted the Elovich equation,suggesting a chemisorption mechanism such as surface complexation formation and that shives surfaces are energetically heterogeneous.Table 3 lists the kinetic constants.In particular,when the concentration increased,the b constant decreased for both SHI-C and SHI-BTCA samples,suggesting a decrease in the availability of adsorption sites for copper adsorption.The analysis of the data clearly indicated that the Elovich model gave the best fit for the experimental data obtained for the SHI-BTCA sample,confirming the involvement of the carboxylate groups in the adsorption mechanism.Nevertheless,the data were also well simulated by the Elovich model for SHI-W and SHI-C samples,indicating the mechanism was complicated with the presence of both chemisorption and physisorption.By applying the Lagergren,Ho and McKay,and Elovich models,it is assumed that the overall adsorption process rate is governed by the rate of binding,whereas when applying the Weber and Morris model,the rate of mass transport is expected to govern the overall process rate.The Boyd model is also an adsorption diffusion model used to predict the mechanistic steps involved in an adsorption process,i.e.,whether the rate of removal of the metal takes place via film diffusion or particle diffusion mechanism.If the plot is a straight line passing through the origin,then adsorption is governed by a particle diffusion mechanism,otherwise governed by film diffusion.An analysis of the literature shows that,in numerous works,film diffusion is the limiting step during the initial stages of the adsorption process followed by intraparticle diffusion when pollutant species reach the material surface.However,it is difficult to estimate appropriate values of Bt for the entire time scale,so the data should be carefully interpreted.The good correlation obtained between the experimental data and predicted curves proved the validity of the Boydmodel only for the SHI-W sample,with R2 values higher than 0.95.For the two other samples,the Boyd model did not adequately fit the data.In addition,as shown in Fig.7,the plots for the three materials did not pass through the origin,revealing that the film diffusion controls the process for the copper adsorption onto three samples.And the properties of AC are also affected by the type of activator, the ratio of added activator, activation temperature, activation time and so on. In consideration of activation difficulty, supply stability and the price of raw materials, AC can be prepared by a wide range of different raw materials.

The use of agriculture byproducts or lignocellulosic materials, such as rice husks and waste newspapers to produce AC has been widely studied. Kazemipour et al., respectively used some agricultural products such as almond, hazelnut, walnut, and apricot to prepare AC Hemp, which can grow quickly in various climates and has various applications is an good choice owing to low cost, economic, and environmental considerations. Hemp, an annual herbaceous plant, as a result of hemp fiber processing technology is rapidly expanding, is widely cultivated in China . However, compared to hemp seed can be refined into biological diesel and hemp bast can be applied in the clothing, respectively. The hemp stems are almost useless and often burned through post-harvest burning of cultivation fields, which not only wastes the resources, but also polluts the environment. Hemp stems are very rich in cellulose and lignin, and have natural nano pore structure. Accordingly, the utilization of hemp stems to produce AC reduce the cost, enhance economic efficiency and contribute to comprehensive utilization of agricultural wastes. There are two processes for the preparation of activated carbons, the so-called physical and chemical activation. The results show that chemical activation has the advantage of high effective and well-controlle porosity. In spite of all kinds of activating agents are used, KOH which can promote AC to produce more pore structure is one of the most widely applied. Rosas et al. adopted phosphoric acid activation to product AC from hemp. A.H. Basta et al. used 2-steps KOH activation to prepare AC from rice straw. However, straw-based material such as hemp stems often have high ash content compared with other agricultural wastes, which are not benefit for the preparation of super AC. As a consequence, preparation and characterization of high performance AC from straw material was studied by few researchers. Not to mention the preparation mechanisms of straws materials-derived AC were investigated. Only Ru Yang et al. investigated characterization of AC derived from biomass source hemp stem via N2, CO2 and H2 adsorption.

Anthropogenic activities, especially those of the industrial and mining sectors, have left considerable areas of heavy metal – contaminated areas worldwide. Due to their nonbiodegradable and persistent characteristics, HMs cause serious soil and water contamination and severe health hazards for living beings upon exposure. In Europe, potentially polluting activities have taken place at an estimated 2.8 million sites, and only 24% of the sites have been inventoried. Currently, only 28% of all registered sites have been investigated, which is a powerful precondition for deciding whether remediation is needed. The term soil remediation refers to actions that are undertaken to limit the extent of soil contamination near hazardous waste sites to prevent exposure to harmful chemicals to people and other life forms. Currently, there are many soil remediation techniques where the most appropriate method depends on the soil characteristics, contamination type, treatment depth and costs involved. As reported by Dhaliwal et al., among the different technologies that are used to ameliorate contaminated soils, phytoremediation is the cheapest and fastest technique to decontaminate soil with HMs. Moreover, phytoremediation has been shown to be a cost-effective and eco-friendly technology compared to physicochemical soil reclamation methods. Metal hyperaccumulator plants can accumulate large amounts of concentrated HMs in their biomass and remain healthy, which makes them suitable for the phytoremediation of HMs in contaminated soil. Among the promising species that have been used for remediating HM-contaminated soils, the use of industrial hemp has shown promising phytoremediation potential in terms of morphophysiological and metal accumulation responses, remediation capacity, trace element phytoextraction and the phytoremediation capability of wild weed. In addition, industrial hemp grows in different climates and produces high biomass yields, and its roots grow deep into the soil, which allows the plant to penetrate deep into the soil and increases the efficiency of removing widespread contamination. Linger et al. found that industrial hemp accumulates HMs in all of its plant parts and that the highest contaminant concentrations accumulate in the leaves. This finding emphasizes the importance of plant management, treatment and disposal of contaminated biomass to avoid secondary pollution, since the methods that are used to recover HMs from plant biomass and/or the safe disposal of harvested plants are still limited. The same study also suggested that in the future, more research must be conducted to provide technological improvements regarding the proper disposal of harvested contaminated biomass. Wu et al. indicate that industrial hemp has been extensively applied, with appropriate pretreatments and investigations, to fields including bioenergy, paper production and construction materials. According to Zhang et al., the postharvest management of plant biomass can be developed, which would include energy production, cannabis drying where the coupling of bioremediation techniques to bioenergy production yields far-reaching social and economic benefits.

Notwithstanding the fact that the phytoremediation of HMcontaminated soil is perceived as an eco-friendly technique, such phytoremediation activities might generate considerable environmental impacts, mainly due to the on-field activities, transportation and disposal or treatment of the biomass. To evaluate the environmental burdens of phytoremediation techniques, life cycle assessment represents a valuable methodology to analyze the in-depth impacts. Other studies have underlined the environmental implications of several bioremediation technologies. Witters et al.found that phytoremediation technologies do not have the energy-consuming and CO2- emitting drawbacks of conventional remediation activities that consist of soil excavation, chemical stabilization, incineration, vitrification and soil washing. Ali et al. also emphasize that conventional remediation technologies may lead to the alteration of soil properties and the disturbance of microflora. In another work, Vigil et al.argued that if the contaminated biomass was not valorized, then the sustainability of phytoremediation was questionable. An LCA methodology was also applied by Vocciante et al. to evaluate the environmental sustainability of phytoremediation technology. The results emphasized the importance of correctly managing the disposal of the contaminated biomass that was produced, where biomass incineration could be more onerous than direct land filling but would be viewed as a more sustainable choice if combined with energy production. Moreover, O’Connor et al. found that phytoremediation at a site was resilient when faced with moderate sea level rises and other hydroclimatic effects that were induced by climate change. Despite the aforementioned studies conducted on phytoremediation, there is a lack of knowledge on assessing the energy and environmental impacts of such remediation techniques. Although the technical issues and suitability of industrial hemp for phytoremediation have been deeply analyzed, less attention has been given to the energy and environmental aspects of the entire supply chain. Despite the growing interest in industrial hemp cultivation, which is also supported by national and European founding and regulations, this ’new crop’ suffers from current limitations, which start with the lack of knowledge of cultivation techniques, concerns by farmers about the legality of cultivation, and the scarcity of product processing plants, especially for the textile and fiber sectors, which limits its diffusion. Moreover, new studies are needed to overcome the current limitations related to the development of more sustainable industrial hemp supply chains. The aim of this study was to assess and evaluate the energy and environmental impacts of growing industrial hemp for the phytoremediation of HM-polluted soil. Additionally, the use of contaminated biomass as an energy resource in 4 different valorization scenarios was also analyzed. The three novel aspects of the performed analysis can be summarized as follows: i) to the authors’ knowledge, none of the previous LCA studies evaluated the energy and environmental impacts of industrial hemp at each phase of the cleanup process; ii) the energy and environmental benefits of phytoremediation were evaluated under 4 different industrial hemp biomass valorization scenarios, which included analyses of different products harvested and different subsystems, such as industrial hemp cultivation in HM-contaminated soils, with and without hemp seed processing, with and without anaerobic digestion of the contaminated products for electricity generation and biomass/digestate incineration in a biomass-fired power plant for electricity production; and iii) the work applied a broad approach in the analyses by including the entire supply chain of industrial hemp for phytoremediation in real sites that were contaminated by HMs.

Selection for genetically stable cultivars with larger seeds will be important for increasing hemp grain yields

The gel point was taken as the time when the sol did not show any movement on turning the container upside down.For analysis of the binder,the left-over sol contaminated with leached out hemp shiv extractives was aged in a container until the gel point was reached and the specimen was termed the “binding matrix”.A schematic illustration of silica glass has been presented in Fig.1.The EDX analysis shows the surface composition of the silica specimens.The percentage of carbon is significantly higher in the binding matrix than the silica glass.The presence of carbon in the silica glass is due to the alkyl groups providing functionalisation.The chemical composition of the silica glass and the binding matrix was determined by X-ray photoelectron spectroscopy.The atomic percentage of various elements present at the sample surface was determined by a low-resolution survey scan.The relative elemental composition for the specimens is listed in Table 2.The main elements detected for both the silica specimens were carbon,oxygen and silicon.The binding matrix showed higher content of carbon as seen in Fig.3.A high-resolution scan was performed on the C1s region for the silica glass and the binding matrix to determine the type of oxygen-carbon bonds present.The chemical bond analysis of carbon was performed by curve-fitting the C1s peak and deconvoluting it into four sub peaks corresponding to unoxidized carbon C1,and various oxidised carbons C2,C3 and C4.The binding energy,corresponding bond type and their relative percentage are listed in Table 3.The silica based binder shows additional oxidised carbon sub peaks,C3 and C4.The C1s high resolution spectra with the deconvoluted peaks for silica glass and binding matrix are represented in Fig.4.The C1 peak is related carbon-carbon or carbon-hydrogen bonds whereas C2,C3,and C4 peaks are associated with carbon-oxygen bonds.The identification of the extracted compounds was performed using GCMS.The polar components of the extractives were analysed for identification of the lipophilic extractives which are responsible for their tacky nature and would contribute to the adhesive properties of the binding matrix.

The yield of total extractives in hemp shiv was 6.23%.The hexane yield and methylene chloride yield in the total extract was 9.05% and 5.00% respectively.The chromatographs for hexane extract and methylene chloride extract are presented in Figs.6 and 7 respectively.All the compounds identified by GCMS are listed in Tables 4 and 5.The individual compounds were identified based on a comparison with GC retention times and mass spectra from the NIST library.Over twenty compounds were identified in the hexane extract and twelve compounds were identified in the methylene chloride extract.For the analysis of the GCMS data,cannabis square pot peaks lower than 30000 counts were rejected.From the chromatograms,it was determined that fatty acids esters,mainly lauric acid and phthalic acid,gave the highest peaks.The compression testing of the composite samples prepared with hemp shiv and binding matrix is imaged in Fig.8 and stress versus strain curves for the before and after immersion samples are presented in Fig.9.The moisture sensitivity of the composite was determined by comparing the mechanical properties of the hemp shiv composite before and after immersion in water for 24 h.Preparation of composite samples using hemp shiv and ethanol-water solution was unsuccessful as the hemp shiv particles were not able to bind.From Fig.9,the results from three test samples before immersion reveal that the composite reaches an average compressive stress of 0.48 ± 0.02 MPa at 30% strain.After the immersion test,a slight reduction in compressive stress by 15% was observed for the three samples and the average reading was 0.41 ± 0.01 MPa at 30% strain.It was noted that further compression led to densification of the sample.After compression,the sample showed some elastic behaviour as seen in Fig.8.In the present study,hemp shiv based composites have been manufactured by using silica sol as a binder.The binding matrix has been characterised and its morphology,chemical composition and physical properties have been studied in comparison with silica glass.

The binder is prepared by the hydrolysis and condensation of TEOS in water in the presence of ethanol as the mediator solvent.HDTMS is added for functionalisation thereby providing hydrophobic alkyl groups in the silica network.The formulation has been used earlier for treatment of hemp shiv particles for imparting hydrophobicity to the material.Here we report the binding properties of silica when mixed with hemp shiv.The silica sol interacts with hemp shiv leaching out extractives and waxes which leads to visual changes turning the silica matrix fromcolourless transparent to yellowish opaque.The silica is able to covalently bond to hemp shiv through the hydroxyl groups of cellulose.During the drying process,the gel starts condensing,releasing ethanol and water and develops a silica network.The extracts from the shiv that are entrapped in the silica network alter the characteristics of the silica.From the SEM analysis,it was seen that the silica morphology is modified.The structure of the new modified silica with incorporated extracts is less brittle when compared to the pure silica glass.The chemical composition of the silica specimens is mainly composed of carbon,oxygen and silicon.Chemical characterisation using EDX reveals that the modified silica has a higher carbon content than the pure silica.Detailed XPS analysis indicates that due to sol interaction with hemp shiv,the silica chemistry has been significantly altered.The surface carbon content of the binding matrix increased by 27%.On the other hand,the oxygen content decreased by 21%.This change in C/O ratio and increase in the surface carbon content can be attributed to the additional extracts that have been identified in the modified network of the binding matrix.The decrease in surface oxygen content can be related to the masking effect of the hemp shiv extracts reducing the detectability of the oxygen bonds in the silica network.The C1s high resolution XPS spectra reveal that the hemp shiv extracts have modified the silica network leading to the appearance of C3 and C4 peaks which are not present in the pure silica glass.Furthermore,the increase in the intensity of the C1 component for the binding matrix from 68% to 84% indicates the presence of CeC and CeH bonds from the incorporated extracts.To analyse the extracts that were leaching out from hemp shiv during the silica based treatment,the process was simplified by using a solution of ethanol and water for the extraction process.

Ethanol is able to dissolve waxes and isolate lipophilic extractives.These ethanol-soluble extractives were analysed using GCMS and it was found that the extract was mainly composed of lauric acid and phthalic acid with many other fatty acids.The majority of the compounds identified using GCMS belong to the group of lipophilic extractives which are hydrophobic in nature.This could possibly be one of the factors for the compatibility between the lipophilic extractives and the sol-gel chemistry due to their hydrophobic nature.The thermal decomposition patterns of the silica specimens were studied by TGA.The binding matrix had a higher weight loss below 100 °C and a greater endothermic peak that can be attributed to the presence of fatty acids in addition to the physically adsorbed water.The embedded extracts in the silica network changed the decomposition range of the organic fragments of the silane corresponding to the temperature range of 270–600 °C.Due to the higher percentage of the organic compounds in the binding matrix,the weight loss was greater and a peak shift was observed in the first derivative of the weight loss thermogram.The maximum decomposition rate in the DTG curve for silica glass was at 520 °C attributed to the loss of silanol groups.The modification of silica network with hemp shiv extracts lowered the thermal stability of the binding matrix.Composites were prepared using hemp shiv and silica sol and their mechanical performance was evaluated.The composites were light weight with a density of 175 kg/m3 and the compressive stress of 0.48 MPa attained at 30% strain is relatively good when compared to other hemp shiv based composites such as hemp-lime,hemp-starch and hemp-clay.Higher strains corresponded with higher compressive stresses leading to densification of the sample without reaching a failure point.This suggests that the interfacial adhesion between the shiv and binding matrix is good and the shear forces are low.After the immersion test,the decrease in mechanical strength can be related to the swelling of the shiv when placed in water for 24 h.Since the binder also provides hydrophobicity to the hemp shiv,the compressive stress versus strain characteristics are not compromised to a great extent.However,the swelling could be related to the slow penetration of water through micro-cracks on the coated surface or due to the presence of small uncovered pores within the hemp shiv.The binder can provide hydrophobicity to the hemp shiv but it cannot fully protect the hemp shiv against long-term water interaction.The slight decrease in compressive stress reached at 30% strain can be attributed to the weakening of the interfacial bonding between the hemp shiv and the binding matrix.However,composites produced using an ethanol-water mixture instead of silica sol was unsuccessful as the hemp shiv fell apart on demoulding.The ethanol is responsible for isolation of the extractives and waxes from hemp shiv but the extractives cannot bind hemp shiv on their own.

The extractives modify the silica chemistry and the binding matrix holds the hemp particles together resulting in the production of coherent composite blocks.When compared to conventional hemp-lime composites,it is evident that the production costs of the hemp-silica composites would be higher due to the hydrophobic treatment on hemp shiv.However,this cost could be off-set by savings elsewhere,both in production ingredients as well as an extension in service life,potentially reducing the whole life cost.Moreover,trim tray the commercial availability of sol-gel solution on an industrial scale would significantly lower the cost of this novel composite.The preparation of hemp-silica composite results in the reduction of 2 L of mixing water per 1 kg of hemp shiv when compared to a conventional hemp-lime composite.The thermal performance of the new composite is expected to be better due to their significantly lower density than hemp-lime.Overall early indications are that the global warming potential of this composite would be approximately 5% lower than that of a conventional composite.The life span is expected to increase by 50% due the improved resistance to water that is responsible for degradation of the composite.Hemp is a genetically diverse and variable crop that produces raw products in three distinct categories: seed/oil,fiber,and metabolites.Within each category,hemp can be improved by multiple avenues of research.We highlight key research areas which increase grower yield or product quality for processors.These topics are not exhaustive,but are intended to guide research to areas which are of the highest priority.Notably,due to the diverse nature of raw products produced from hemp,research targeting hemp yield traits will improve our understanding of basic plant biology.Seed and oil research will enrich our comprehension of grain yield and composition.Research into hemp fiber will enhance our knowledge of stem development and composition,genetic regulation of fiber traits,and biofuel production.Studies targeting metabolite yield will expand insights into both Cannabis-specific and shared plant chemistries,interaction with biotic stresses,and trichome development.Investigations into the plasticity of hemp’s sexual phenotype will contribute to identifying mechanisms underlying plant sex determination.Importantly,unlike previously domesticated crops,selection for increased hemp yield provides a unique opportunity to study plant domestication for grain,fiber,and chemistry traits.With hemp,unlike most other crops,these valuable characteristics can be studied within a single species for which they are essential to sustainable and profitable production.As a semi-domesticated crop,many traits for hemp seed and oil yield require improvement; these include seed size consistency and improved shattering resistance.Significant advances in hemp seed production occurred with the development of FIN-314 ,an auto flowering grain variety with a short stature,adaptation to high latitudes,and high yield,resulting in it presently being the most popular cultivar grown in Canada.However,seed size is highly variable among hemp cultivars and ‘Finola’ seeds are 50% the size of many commercial varieties.During domestication,hemp has retained little resistance to shattering.However,hemp field trials have revealed that significant grain is lost due to shattering prior to and during harvesting as a result of inconsistent inflorescence maturity ,particularly if collected outside of the optimal harvest time windows.To mitigate this problem,growers harvest seeds at 70% maturity ii.Hemp inflorescences are large multi-seeded heads in which each individual seed is partially surrounded by a bract,and an abscission zone connects the hull to the pedicle.Selection for a stronger-walled abscission zone or the prevention of bracts releasing seeds are possible physiological traits to target to reduce hemp seed loss due to shattering.Furthermore,immature seeds are similar in size,but weighed only half that of mature seeds due to incomplete embryo development.

The addition of heavy metals and Sb significantly affected the growth of all three hemp varieties

Compared with the control,Ni110 significantly reduced the hemp emergence rates for the three hemp cultivars,and Ni220 even completely inhibited germination.Unlike Ni stress,Pb1500 had no marked effects on the emergence rates for any of the hemp cultivars compared with the control,however,Pb3000 significantly increased the rates of Guangxibama and Yunma No.1.Both Sb50 and Sb100 significantly increased the germination rate of Guangxibama compared with the control,however,no marked differences between treatments for rates were found for the other two cultivars.Husain et al.also reported a reduction in seed germination of six hemp varieties sown in mine soils and most of the germinated plantlets died one to two weeks after their emergence.Heavy metal and Sb stresses significantly negatively affected the plant height,stem diameter,and the number of leaves of flax.For Cd,Ni,and Pb,most measurements of the plant height,stem diameter,and the number of leaves of the three flax cultivars were significantly reduced by both treatment levels,and the negative effects increased with increasing stress level.In general,compared with the control,Y2I329 was affected only slightly by the different levels of Cd because the three morphological indices of Y2I329 changed the least under Cd stress.Similarly,under the stress of Pb,Y2I329 still showed the best endurance.The plants under high Ni treatment died,and similar negative effects of Ni in flax were also reported by Amna and Syed.The effects of Sb on flax are complex and there is no uniform rule.Plant height was the least affected.The plant height,stem diameter,cannabis grow equipment and the number of leaves of Guangxibama and Yunma No.1 were significantly or slightly reduced by Cd stress compared with that of the control.Similar results were also observed by Luyckx et al..Treatment Cd40 increased the plant height of Zhongdama No.1 but Cd80 significantly reduced it; no significant difference was found for stem diameter and number of leaves.Treatment Ni220 completely inhibited the growth of the three hemp varieties; Ni110 significantly reduced the three morphological parameters for all varieties of hemp.

Pb addition at both levels significantly or slightly reduced plant height,stem diameter,and the number of leaves of all varieties.Sb did not significantly affect the plant height of Guangxibama and Yunma No.1 but significantly increased this characteristic for Zhongdama No.1 compared with that of the control; Sb had no marked effects on the stem diameter of hemp except for the significant reduce in Yunma No.1 by the Sb50.Treatment with Sb50 showed no significant effects on the number of leaves for Guangxibama and Zhongdama No.1 compared with the control but significantly reduced that for Yunma No.1; Sb100 did not significantly affect the number of leaves for Guangxibama and Yunma No.1 compared with Sb50,but notably reduced them compared with the control; Sb100 markedly increased the number of leaves compared with that for Sb50.Cd stress significantly reduced the fresh biomass of HP,but no significant reduction was found for Hongyou No.2 and GGS compared with the control.No significant difference in fresh biomass of the three kenaf varieties was found between Cd40 and Cd80.The addition of Ni and Pb notably or slightly reduced the fresh biomass of all three kenaf varieties compared with the control,and the reduction of biomass increased with increasing metal concentration.Similarly to its effects on flax,Sb50 significantly improved the biomass of all kenaf varieties compared with the control; Sb100 notably or slightly reduced the biomass compared with Sb50 but still increased the biomass compared with the control.Nickel was not lethal for kenaf varieties,however,it significantly inhibited plant growth.Lead was the second most toxic element,especially Pb3000,followed by Cd and lastly by Sb.Concrete is the single most widely used material in the world.Due to the worldwide substantial expansion of our built environment the demand for cement,as a par excellence material used for concrete production,will significantly increase in the near future.For cement production,huge exploitation of Earth’s minerals precedes.Its production is also an energy-intensive process,which contributes to high pollution,especially carbon dioxide emission.Since the increase in global carbon dioxide emissions is unacceptable,a search for other binder alternatives is necessary.

The solution for cement substitution or even its total replacement could be found in industrial by-product pozzolanic materials.Until now,the mostly used pozzolanic material for cement substitution is fly ash that comes from thermal power plants after coal combustion.When fly ashes are mixed with an alkali activator,they form alkali-activated material.This group of materials is comparable in physical and mechanical properties with cementitious materials,but has better durability and can come even at a cheaper price,leaving a much lower environmental footprint.However,these materials still do not have a broad usage in the building construction.The standardization of their solid based materials and activators should be firstly defined.Besides,there are also some disadvantages of the materials that should be solved before they find a broad usage on construction sites.AAMs are brittle or quasi-brittle materials and to move toward more ductile behaviour they need to be reinforced,similarly to cementitious materials.In the field of fibre reinforced materials,natural fibres have attracted a lot of attention in the last decade due to their low production cost and low consumption of energy during their production.Natural fibres are fully biodegradable,renewable resources and globally available.Their tensile strength and E-modulus are comparable to those of synthetic fibres.However,the mechanical properties of natural fibre reinforced composites are somewhat weaker compared to their counterpart reinforced with synthetics fibres.Natural fibres are generally nonhomogeneous,have high hydrophilicity and reduced long term durability in the matrix.One of the most distinctive parameters influencing the properties of the composite is the characteristic of the fibre/matrix interface itself.The quality of the bond is related to the fibres’ surface morphology and topography.To optimise the bond,so far in cementitious composites various chemical treatments on the surface of natural fibres have been applied.In terms of its simplicity and effectiveness,sodium hydroxide treatment could be a viable treatment also in AAMs.There are no results of the hemp fibres’ surface roughness changes and their influence on the pre-and post-peak of the flexural stress–strain curve,after the usage of the sodium hydroxide treatment.However,the enhancement of the fibres’ physical and mechanical properties when the fibres are treated with sodium hydroxide is confirmed.The researches on the alkali-treated fibres show that 5% sodium hydroxide solution treatment of hemp fibres resulted in the fibres’ density increase ,since the treatment cleans the impurities from the fibres’ surfaces.

The treatment also increased the tensile strength and Young’s modulus of the hemp fibres for ca.4% and 28% respectively.Mwaikambo and Ansell tested mechanical characteristics of the hemp fibres after treatment with 0.03%,0.08%,0.16%,0.24% and 0.32% of sodium hydroxide solution.They stated that there was an increasing trend in the tensile strength of the fibres after increasing the concentration of sodium hydroxide.The fibres’ highest tensile strength is reached after the usage of 0.24% of sodium hydroxide.The usage of the concentration of 0.16% of sodium hydroxide solution resulted in the fibres’ highest Young’s modulus.The highest concentration of sodium hydroxide provided the highest fibres’ strain at failure.Alawar et al.showed that data palm tree fibres treated with 1% of sodium hydroxide increased their tensile strength by 300% compared to non-treated fibres.Up to 11%,higher tensile strength of the kenaf fibres after the treatment with 6% sodium hydroxide is achieved in the research conducted by Edeerozey et al..After treating the jute fibres with 0.5% sodium hydroxide solution,the tensile strength of fibres increased by 82%.The sodium hydroxide treatment of natural fibres proved to be very efficient in enhancing fibres’ mechanical characteristics.However,there is no published work on the influence of the sodium hydroxide treated fibres on any group of alkali-activated mortars.According to the authors’ knowledge,there are only the works conducted by Amalia et al. and by Sean et al.where previously treated short natural fibres are used in alkali-activated matrices.In both works,natural fibres were used,but none of them used hemp fibres.Additionally,both studies focused on the alkali-activated pastes,having no aggregates in the matrix.Due to the pure mechanical characteristics and high cost of the pastes they should be upgraded to composites containing aggregate to be considered as building materials in civil engineering applications.Very importantly,the work conducted in this study is the first research dealing with the durability of the natural fibre reinforced alkaliactivated materials in terms of wet/dry cycles.Composites reinforced with natural fibres show comparable mechanical properties tested at an early age as their counterparts reinforced with synthetic fibres.However,after some months,natural fibres degrade in the alkaline environment and their long-term physical and mechanical properties are questioned.Therefore,it is extremely important to estimate the durability of the natural fibre reinforced high alkaline materials.Only with a proof of their durability,they can find a broader usage in the replacement of some traditional fibres and the usage where high energy absorption capacity,mobile grow system resistance to impact- and dynamic loading or prevention of cracking is required.The objective of this research was to study the physical and mechanical properties of hemp fibre reinforced alkali-activated materials before and after wet/dry cycles.The constant change of the relative humidity can seriously attack and destroy the fibre–matrix interface,which reduces the composite’s mechanical properties.With the wet/dry cycles we wanted to simulate a real weather change for the specimens that could be exposed to outdoor environmental conditions and to examine the composites’ properties change.Additionally,the influence of sodium hydroxide surface treatment of hemp fibres on the physical and mechanical properties of fly ash-based alkali-activated mortars was examined.Three different concentrations,i.e.,3%,6% and 9% of sodium hydroxide treatment were applied on fibres and the mortars’ porosity,water absorption,bulk density,compression- and flexural strength,as well as energy absorption capacity under flexure,prior and after the wet/dry cycles,were measured.Besides,the X-ray Powder Diffraction and Thermogravimetry-Differential thermal analysis were conducted on the mortars.

To estimate the fibres surface changes after the treatment,Scanning Electron Microscope and Atomic Force Microscope are used.In addition,the water absorption of the fibres was measured.For fibre reinforcement,primary bast hemp fibres were used Hemp fibres were selected since they are widely used as fibre reinforcement in cementitious materials and have a long cultivation tradition in Europe.Their properties are listed in Table 1.The fibres length and dosage were chosen based on the literature review,as optimal values for a compromise between mechanical properties in hardened state and fresh state properties such as work ability and fibres good dispersion within the matrix.To cut fibres to the length of 10 mm,a small bundle of fibres were taken,measured with a ruler and cut with scissors manually.Due to their hydrophilic nature,the fibres were added to the mixture in water-saturated dry surface condition.They were completely soaked in water for 24 h,taken out,softly squeezed by hand and their surface was wiped with a cloth.The water absorption was measured on 200 g of fibres.From a fibre bundle,fibres were separated manually,and their weight is measured firstly in a dry condition.Afterwards they were put in water and on defined time intervals their water absorption was measured.Even though it could be seen that the fibres’ highest water absorption happens within the first 20 min,they were left in water for 24 h in order to be fully sure that they absorbed maximum water they could.It is measured that the weight of the water-saturated non-treated fibres is 2.3 times the weight of the dry fibres.Due to the ease of application,effectiveness of the fibres’ structure and surface change,availability of the material for fibres treatment,the sodium hydroxide was used for fibres treatment.The sodium hydroxide was also used within the composites’ activator and it was not necessary to additionally provide a new material for fibres treatment.It is true that sodium hydroxide has a negative environmental footprint.However,there is a very minor amount of the sodium hydroxide that could be used for the fibre treatments.In this context,it should be noted that NaOH is the main activating agent for other types of alkali-activated materials bound in a hardened matrix,which has been documented in the publications or even applied in practice.Besides,natural fibres have enormous advantages over traditional fibres.Not only regarding the environmental footprint,but also that they are renewable materials.Therefore,even though they are not used as raw materials,their usage within the composites in the research is still justified.For fibre treatment three different concentrations of sodium hydroxide solution were used: i) 3%-; ii) 6%- and iii) 9% sodium hydroxide solution.To obtain the required sodium hydroxide concentrations,185.57 g,382.98 g and 593.41 g of sodium hydroxide were dissolved in 6000 g of distilled water respectively and left for 24 h to homogenize.Three plastic containers were half-filled with respective sodium hydroxide solutions.Afterwards,in each container 100 g of hemp fibre bundles were added,the containers were filled completely with sodium hydroxide solutions and tightly closed.The containers were placed in a drying oven at 80 ◦C temperature for one hour.

Hemp fibres were used for manufacturing sails and ropes

The increase of phosphorus in the minesoil was in line with organic matter content increase.Soil organic matter plays an important role in P sorption as the main constituent of the soil sorption complex which is responsible for binding of anions in the soil material.Phosphorus leaching can be significantly affected by soil adsorption-desorption properties,and it has been shown that application of organic fertilizers could significantly improve the soil phosphorus adsorption capacity.Mengmeng et al.found,that organic fertilization together with mineral NPK increased available phosphorus by 150 % comparing to NPK alone.Application of organic matter is also supposed to improve the soil phosphate availability by promoting microbial activity.The increase in potassium content was slowier than that of phosphorus.During the first three years,this increase was not statistically significant.It was only in 2017 that a statistically significant increase in the potassium content was noted,to the level of 95 mg kg of soil.In the last year of the experiment ,the potassium content reached the value within the norm for this element,ranging from 120 to 200 mg,reaching the value of 175 mg kg of soil.Disturbance to soil by mixing subsoil with topsoi may decrease potassium content.In the studied soil the initial amount of K was very low.On top of that it is known that potassium readily leaches from organic matter as it decomposes.found,that when staw was left on the field,most of its K content was leached during the first month of storage.That can explain the delayed increase of this element level in the course of soil remediation – even though annual potassium fertilization was used.On the other hand hemp is known to take up potassium when the element is not needed and hemp has a lower requirement for potassium than other crops.Most of the absorbed potassium absorbed by Cannabis is concentrated in the stem.

That could explain the finally observed increase of the potassium in the studied soil as this part of the plant is particularly resistant to decay due to the high content of celulose and lignins and could store the absorbed amount of potassium.It is worth noting that the content of phosphorus and potassium reached a value above the lower limit of the norm for these elements only after three and four years of soil rehabilitation respectively,cannabis grow tent despite the annual intensive fertilization with these elements.This confirms the important role of organic matter in the absorption of potassium and phosphorus in the soil.A significant increase was also observed in the case of magnesium content.In the base year,the magnesium content was below normal and amounted to 40.6 mg kg of soil.The level of macro-nutrient gradually increased and in 2017 it amounted to 92 mg / kg of soil,reaching the value of 119.2 in the last year of the study.The standard for the content of magnesium in the soil is from 61 to 100 mg kg.The rate of movement of magnesium in soil depends on soil texture,rainfall and soil pH.It is generally believed that it is easy to migrate in neutral to acidic soil and difficult to migrate in alkaline soil.That suggests that soil conditions in the course of the experiment were in favour to limit leaching of this element and as a result progressive absorption within the organic matter delivered into soil.The manganese content in the tested soil increased in the years 2015–2017 as reclamation was carried out and fell within the norm,which is from 85 to 830 mg.This increase was statistically significant.Also,comparing the base year with 2017,a significant increase in the level of manganese in the studied soil was observed.It has been reported that soil Mn was primarily found in the exchangeable and organic fractions,regardless of soil pH but solubilization of organic acids under alkaline conditions may result in increased complexation of Mn inhibiting its precipitation in the soil environment.It has been also observed that stronger bonding of manganese ions by organic matter was induced by increased soil pH.These previous observations well explain our results showing that Mn content in the soil directly followed changes in the soil pH.The boron content in the soil varied in the studied period.Its level increased significantly from 0.41 mg/kg of soil in 2014 to 0.99 mg/kg of soil in 2017.There was no significant change in the boron level between the starting year 2014 and 2015.Between 2015 and 2016,a significant increase of this micro-nutrient content was observed.Despite the increase,the content of this micro-element was below the standard for Polish soils,which ranges from 2.2 to 7.2 mg kg of the soil.

Although many investigations have been performed with the influence of certain constituents on boron behavior in soil,there is no general agreement on the role they play in B adsorption and desorption.There is general belief that organic matter plays an important role in B adsorption and its availability in the soil.Besides organic matter,also soil pH plays an important role in B behaviour in the soil environment.Gu and Lowe found that B adsorption by humic acids was strongly pH-dependent,being low and relatively constant in the pH range 3.0–6.5,increasing markedly up to a peak at near pH 9.5,and then decreasing at higher pH values.It has been concluded that complexation of B with soil organic matter should only be important at alkaline pH.Our results are in agreement with those previous observations.We have noted the increase of B content in the minesoil together with organic matter accumulation and with soil pH increase.In recent years there has been a development in many areas of plant fibre-based materials ,which has led to an ever-increasing demand for flax scutched fibres,particularly in Europe,which produces 80 % of the world production of flax and hemp.A study conducted by ADEME,the French environment agency,in 2015 predicted that it would be necessary to sow 145,951 ha of fibre crops in France by 2030 in order to meet the demand.This would represent about 1,000,000 tons of straw.In 2018,a total area of only 107,000 ha of textile flax was cultivated in Europe,including 89,000 ha in France.Due to the need for a mild and humid climate and long crop rotations with flax cultivation being repeated on the same land only once every six to seven years to avoid soil depletion and the proliferation of diseases ,the traditional flax production areas are at their maximum production capacity and cannot satisfy an ever-increasing demand for flax fibres.It is therefore necessary to find an additional crop to increase the production of high added value fibres for textile and technical applications to reach the targeted surface of 145 000 ha suggested.In the past,hemp was cultivated for such applications ,in particular for the rigging of sailing ships.A decline in its use during the 20th century led to a sharp decrease in its cultivation worldwide.Hemp cultivation in Europe rose from 15,000 ha in 2013 to 47,000 ha in 2016,of which 16,400 ha in France.A study conducted by FRD and whose results were published in an ADEME report showed that 200,000 ha of hemp is likely to be cultivated in France in the future for different end uses such as fibre,cannabidiol ,shives for building,but this work only investigates the production of long line fibres.

Indeed,unlike flax,hemp is adapted to the climatic and soil conditions of most areas of France and Europe,which allows its establishment over a large geographical area in Europe or in many places in the world such as China.However,the possibility to perform dew retting advantageously is more favourably conducted in mild and humid areas even though it was shown it can be conducted in many different European climates with increased durations for example.The textile flax production zones in Europe where the extraction capacity by scutching/hackling is already present corresponds to the most favourable zone for dew retting of flax and also for hemp.Hemp could also be favourably inserted within flax crop rotations due to its limited fertilizer and pesticide requirements and for its competition against weeds.In the 19th century,harvesting was performed mainly by hand in Europe and in China.In Europe,the first machines to perform fibre extraction using breaking rollers and beaters appeared in 1820.In Eastern Europe,hemp was mainly cultivated for textiles for its long line fibres and countries such as Hungary and Romania developed specific scutching and hackling devices to extract the fibres.These machines,however,required as input,well-retted stems.Water retting was traditionally performed prior to fibre extraction.These processing lines could process whole hemp stalks and very long line scutched fibres could be obtained.However,the resulting fibres were subsequently cut into sections of about 70 cm to be hackled on flax machines.These devices are now very old and have been decommissioned for their dependency on water retting that has been banned in most countries due to its high environmental impact and the risk for humans and animals health.Moreover,the hemp industry in Eastern Europe was labour-intensive,particularly for the harvesting stages and this negatively affects the economic sustainability of traditional value chains.Indeed,the hemp sector has not been able to draw inspiration from the mechanisation of the flax sector and there is currently no complete mechanised hemp harvesting chain for long line hemp fibre production.China,for its part,has invested considerable resources to modernise and recreate an economic sector entirely based on the flax value chain and field retting.This means using flax machinery for the management of the harvesting and fibre extraction.However,this requires that the stem length is shorter than 1 m.In the field a hemp mower,grow lights for cannabis a swath turning machine to homogenise the field retting and an adapted baling system are necessary.

A similar production system proved to be technically feasible in the early years 2000 with the “baby hemp” cultivation in Italy ,where stems were kept short by applying an herbicide when the plant was approximately 120 cm high.In China,manual labour is still used to perform dew retting management and cutting hemp stems in 1 m pieces.If in the past,the numerous attempts to develop hemp harvesters were not completely satisfactory ,suitable hemp mowers are now on the market.However,a machine to cut on the field the mown stems is still not available but this is necessary if flax turning and bailing machinery is to be used.This type of machine is under study and advanced prototypes were tested in summer 2021 with a global success even though improvements need to be completed.With the success of such a prototype,a complete value chain could be created using flax processing lines.Nowadays,hemp fibres for paper pulp,or insulation materials are extracted using hammer mills.This process is very efficient but it damages the fibre and reduces its length.Hemp fibre price,used for technical non-structural automotive applications,is generally much lower than the price of scutched textile flax.However,the mechanical properties of hemp fibres extracted using a hammer mill remain generally low.These fibres cannot be used for load-bearing applications.The possibility to obtain load-bearing grade fibres from hemp would open a complementary market to the one of flax fibres,which is globally saturated and guarantee a higher price than that for the fibres extracted using hammer mills.Ideally,this price should be lower than that of flax long line textile fibres,too expensive for numerous applications in the automotive or other industries.As mentioned above,the old East European hemp scutching and hackling lines are no longer operating,and only flax dedicated equipment are available industrially to extract long line fibres.Preliminary scutching and hackling trials of hemp stems on industrial flax lines were performed by with low scutching yields of long line fibres and high amounts of scutching tows.Vandepitte et al.also used industrial scutching facilities with some of the process parameters changed for hemp extraction purposes with a wide range of European hemp varieties.Higher levels of long fibre scutching yields were globally obtained but this one was dependant on the batches/varieties/levels of dew retting.Following scutching,hackling is generally performed to start the division of technical fibres.During this process tows may also be generated.In hemp stems,the mass of fibres represents,depending on the varieties,about 30–35 % of the mass of the stem.To value the hemp straw and particularly its fibres in the most advantageous way,it is essential to maximise the amount of long line fibres obtained at the end of the extraction process.Main objective of this work is to investigate if hemp could become a source of long line fibre for load bearing composites in complement to the flax ones.To reach this objective,this study proposes to study the long fibre yields obtained at the end of the scutching/hackling process and the quality of fibres that can be obtained.

Plants with the secondary fibre front just reaching stubble height  could be considered ideal

This has implications for the development of multi—purpose cropping systems of hemp.While low quality fibre can be extracted from plants gro̶wn primarily for their seeds or chemicals derived from inflorescences,the extraction of high-quality textile fibres requires harvesting when no seeds or inflorescences are present yet.Fibres from socalled multi—purpose hemp grown for seed and fibres will thus always contain a mixture of short and long fibres.Plants of increasing height and weight in Fig.6 could represent the same plant at different moments in time,but they can also be considered different plants in a crop at the same time,because with respect to primary  and secondary fibre development,individual plant size is the key factor,not the moment a particular height or weight is reached,or the phenological stage.The stem part that is valuable for textiles,the stem part between the dotted lines in Fig.6,is located higher up along the stem with increasing plant size.It is supported by a stem base of increasing length and weight,which is unfit for yarn production due to the presence of secondary fibres.In short plants  a share of the primary fibres,though fit for yarn spinning,is lost in the stubble,which in practice is 15–20 cm.Once the secondary fibre front surpasses the stubble height  part of the primary fibres are contaminated by secondary fibres.The lower in the plant or the heavier the part of the stem above,the thicker this unwanted fibre layer is likely to be.For reasons of simplification,the inflorescences of the plants in Fig.6 have equal lengths for all plants,it could however be expected that this part becomes gradually longer with increasing plant size.However,vertical grow system no data were recorded.

Mediavilla et al. showed in a dioecious variety that the accelerated development of secondary fibres around flowering first takes place in female plants and later in male plants.This makes sense,when the increasing weight is considered the cause of secondary fibre formation.Male plants on average are longer,but the female inflorescences,where the seeds are gradually filled,are likely to have a higher weight.Bócsa and Karus  also stated that female plants have a relatively higher secondary fibre content than male plants.The proposed conceptual model  also implies that homogeneity with respect to plant size is important when growing hemp for textile uses.In stands with plants of different heights the valuable ‘middle section’ is at variable height,which would cause difficulties in harvesting and processing.The tops of the plants are the comparable parts,not the bottom parts.According to both Fig.4  and 5,secondary fibres above stubble height in Futura 75 can be avoided when the crop is cut when plants are around 1.3–1.4 m and not yet flowering.It is likely,however,that this height is different for varieties,as secondary fibre development is reported to be different between varieties.Reported differences,however,could partially be due to size differences as well.For this reason true varietal differences and differences caused by size differences should be disentangled in future experiments.A non–flowering crop with a height of 1.3–1.4 m can be grown in about two months when hemp is sown at a normal sowing date in April under Dutch growing conditions.However,a subsequent second fibre hemp crop,to compensate for the relatively low stem dry matter yield of the short crop,will be a challenge.For a first sown crop,varieties can be chosen based on excellent fibre qualities,for a possible second crop the variety should be late flowering and it should also have an inherently low secondary fibre content.Further the soil has to be prepared into a homogeneous seedbed again and in dry years irrigation might be necessary to achieve even emergence.Due to the drier summers and shorter days a second crop seems less realistic in Italy than in The Netherlands.However,even when technically possible,it should be economically sound as well,which is doubtful as yet.An advantage of a short crop is that the stems could be processed on existing flax  processing lines as the limited market for high‒quality hemp yarns as yet does not justify the development of specialised hemp scutching and hackling lines.Such systems are dimensioned for flax ribbons with a length usually between 80 and 120 cm,which is about the length of the useful middle section of the stems in our experiment.Earlier attempts in Italy to produce smaller hemp plants by stopping their growth with glyphosate at the desired plant height of 1.2 m  failed due to the environmentally unfriendly production methodology,low yields,low quality,and high costs.Westerhuis et al.,however,showed that normal amounts of scutched long fibres can be extracted from smaller plants.However,these fibres were not hackled.It is likely that the early harvested short crop that we need to avoid secondary fibre formation has relatively fine primary fibres as well.

Fibres have been reported to be finer with decreasing plant size or conditions that in general cause smaller plants,e.g.,earlier harvest or increasing sowing density.Also with respect to the unwanted lignification of the fibres an early harvest before flowering seems best.For future research on this topic it has to be considered that between individual plants of the same height or weight relatively large differences exist in the height of the secondary fibre front.This was not only caused by the fact we measured once every 10 cm stem length; in the field experiment where three cuts were made in every internode a comparable spread was observed.Differences between plants  and,e.g.,wind would co-determine the actual forces  along the stem and thus the mechano perception  inducing fibre formation.Further,we should keep in mind that countering the forces the plant is subjected to,means countering the fresh weight,not the dry weight we measured hence plant fresh weight should be measured as well.To study the effect of weight on secondary fibre formation in more detail,plant weight could be increased artificially.Cannabis sativa L. has been used for more than 6000 years as a source of food, fiber, oil and medicine, as well as for recreational or religious purposes . Cannabis has a very complex chemical composition, with around 540 reported specialized metabolites, such as cannabinoids, terpenoids, flavonoids and alkaloids. The most active of these are by far the cannabinoids, a class represented by more than 100 known terpenophenolic compounds that accumulate mainly in the resin secreted from the trichomes of female plants . Based on its use, cannabis can be technically divided into two distinct groups: marijuana and hemp. Traditionally, marijuana is almost exclusively grown in greenhouses or other controlled environment facilities, being primarily bred for its main psychoactive cannabinoid, Δ9 -tetrahydrocannabinol . On the other hand, hemp serves more as an agricultural commodity, being valued for its fibers and seeds and, more recently, for its nonintoxicating medicinal compounds, notably cannabidiol . From a legal point of view, in most European and North American countries, cannabis is classified as hemp if the crop contains less than 0.2−0.3% THC . Due to their low THC content, hemp and CBD products have recently gained an increased popularity, as their attributed medical benefits are achieved without the “high” effects of marijuana . Consequently, a wide panel of products are nowadays marketed as “full-spectrum” formulas, dietary supplements or CBD-enriched products . The presence of pesticides in hemp crops is a very challenging issue nowadays, not only for cultivators, but also for regulators, consumers or public health researchers .

Many studies have revealed there is no clear relationship between pesticide use and augmentation of cannabis yields, being repeatedly claimed that their role in weed and pest control might be actually unnecessary . Beside their concealed use during cannabis growth, other reasons for pesticide contamination might be related to the spray drift from adjacent crops or assimilation from the contaminated soil; numerous pesticides are environmentally mobile, being carried away by groundwater and rain, whilst cannabis is recognized as a robust and fast growing plant able to absorb pollutants with a great efficiency . Thence, pesticide contamination of cannabis materials has been repeatedly brought into attention . A survey of 389 cannabis products from the state of Oregon found 24 residual pesticides, with piperonyl butoxide as the most commonly retrieved contaminant. Furthermore, 12 pesticides were found in up to 50 % of the cannabis samples collected from central Californian dispensaries . Out of 26 investigated cannabis samples, 84.6 % were confirmed to be positive for pesticides from various classes, such as insecticides, miticides, fungicides or growth regulators . In addition, a multi-screening study testing for 71 residual pesticides in various cannabis products from Italy revealed that amitraz, chlorpyrifos and trifluralin were above the acceptable residual limits set at 0.010 mg/kg . Nevertheless, occupational or non-occupational exposure to residual pesticides has become an important issue due to potential adverse health effects. For example, organophosphate pesticides, mobile grow systems such as chlorpyrifos, malathion, parathion methyl, ethoprophos or coumaphos, have been found to be highly toxic, inducing neurobehavioral and cognitive disorders, teratogenicity, immunotoxicity or endocrinal and metabolic disturbances . Daminozide and paclobutrazol are two plant growth regulators that have been banned in the USA and numerous European countries, due to their carcinogenetic properties; however, both have been found as contaminants in cannabis products . In this light, more and more regulatory agencies are addressing the residual pesticides issue in cannabis products. For example, in the USA, pesticide regulations are specific to each state, mostly due to the fact that cannabis cultivation is still not yet federally legal.

Among the states, California has the most severe requirements, monitoring 66 pesticides, followed by Oregon with 59 pesticides. In comparison to these, Canada has set wider and stricter controls of pesticides in cannabis products, demanding testing for 96 pesticides, with limits of quantification usually lower than those set in the USA . From a processing point of view, cannabis derived extracts are frequently obtained using CO2-supercritical fluid extraction followed by winterization , decarboxylation , distillation and, optionally, a chromatographic-based method for the isolation of specific cannabinoid compounds . For instance, CBD purification is mostly achieved by recrystallization, conventional chromatography with solid stationary phase or liquid-liquid chromatography. LLC, better known as centrifugal partition chromatography and counter current chromatography , is a preparative separation technique where the two phases of a biphasic solvent system are used as the mobile and stationary phase. One of the two phases is kept stationary inside the column with the help of a centrifugal field, while the other one is pumped through the column . In this sense, LLC enables high column loading, while expensive solid stationary phases and time intensive column packing procedures are not required. In addition, the almost limitless variety of possible biphasic solvent systems and easy preparation of tailor-made solvent systems make LLC a very flexible, scalable, as well as selective separation technique . Taking advantage of these benefits, Hazekamp et al. showed that CBD can be separated by CPC using n-hexane/acetone/acetonitrile 5/2/3 as a biphasic solvent system, with the acetonitrile-rich phase as the stationary phase . To this end, a considerable attention has been paid either on the large-scale purification of CBD by LLC or the ultra-trace detection of residual pesticides in cannabis products, but not to the removal of the contaminating pesticides. Therefore, the aim of this study was to establish a systematic computer-aided approach for the selection of biphasic solvent systems for the simultaneous purification of CBD from hemp extracts and removal of specific-contaminating pesticides. In this sense, a predictive thermodynamic model was used for solvent system screening, guiding the user toward the design of tailor-made solvent systems for the isolation of pesticide-free CBD from a particular hemp extract using LLC. Two experimental protocols were followed in the shake-flask experiments, depending on the purpose. For the initial screening of the partition coefficient of CBD in different solvent systems, 5 mg of hemp extract were added to upper and lower phases of preequilibrated solvent systems and placed into a 20 mL vial. Then, each phase was analyzed by HPLC-DAD . Once the three solvent systems were selected, the six pesticide mixes and CBD standards were combined together and a stock solution, in which CBD and each pesticide had a concentration of 50 ppm, was obtained by a proper dilution in acetonitrile. 20 μL of the stock solution were added to 20 mL of each of the three selected solvent systems, affording a nominal concentration of 50 ppb of each solute. Afterwards, 1 mL of upper phase and 1 mL of lower phase were taken, evaporated to dryness, re-dissolved in 1 mL methanol and analyzed by LC–MS/MS to determine the concentration of each analyte in the phases.

The RILEM protocol is applied to around 100 g of particles to obtain this parameter

These functional properties are the result of the vegetal aggregates employed in the formulation,whilst mechanical strength is provided by the presence of frame.Numerous studies have been carried out on defining and understanding the properties of the material,or optimising the formulations used.A number of recent studies have looked at the durability and long-term behaviour of these insulators,but the accelerated aging processes are much too short or overly severe in comparison to real-world conditions of use,such as the application of freeze–thaw cycles.However,lack of knowledge about the evolution of the properties of plant-based concretes over time is a barrier to the development of these materials.Indeed,the lack of guarantee as to the durability of the desired properties over a given period of time does not inspire confidence in users,architects or insurance companies.It is for these reasons that a study is conducted on the durability of hemp-based concretes,with the aim of identifying the mechanisms which cause the functional properties of the material to change.However,to date,there has been no study done of the change over time observed in the plant aggregates on their own,although it is these particles which are responsible for a large proportion of the properties for which the material is used.In order to understand the mechanisms of aging of plant-based concretes,it seems essential to understand the behaviour of the particles in bulk over time.With a similar chemical composition,made up of cellulose,hemicellulose and lignins for the most part,it is possible to draw inspiration from the numerous studies examining the durability of wood.

Durability studies on wood have produced standards which guarantee quality and users’ expectations over a given period of time,mobile vertical rack in set usage conditions and with an amount of maintenance.Depending on the application,specific wood species are chosen according to the applications and the conditions of use.Various aging factors are applied on wood in these studies,such as immersion in water for periods from 10 days at 60 and 90 °C to 8 and 2000 years in natural conditions,variations of relative humidity during 20 days to one year,exposure to UV aging until four weeks or natural aging without protection during several years.Therefore,depending on the study in question,the aging conditions are very different in terms of environment or exposure duration.Whatever the protocols used,the functional properties are monitored over time,namely mostly mechanical and/or hygroscopic properties,but also acoustic properties.Overall,aging leads to deterioration in the mechanical properties and to an increase in water sorption capacity.Other parameters which characterise the microstructure of the material are also studied,such as porosity,swelling,or variations in weight of the materials.The variations of functional and microstructural properties are often explained by a change in the chemical compositions of the wood,usually due to the degradation of the lignin or hemicellulose.These chemical degradations may result from photo-oxidation or thermo-oxidation reactions,but above all,from the action of micro-organisms which can grow on lignocellulosic materials in high humidity conditions.Indeed,the micro-organisms use the cellulosic materials as a nutrient,and they may,selectively or otherwise,attack pectin,lignins,hemicellulose or cellulose.These micro-organisms are present in the air and in water,but also in the plants as they grow.Indeed,in order to separate the fibres from the stalks more easily,the material may be retted for a time,enabling the micro-organisms to consume the pectin which binds the fibres together.Therefore,such retting impacts upon the properties of the materials.There are various tests of resistance to the growth of micro-organisms,placing the plant materials inoculated with moulds in conditions of high hygrometry,as for example 26 °C and 85 and 95% RH,or 20 °C and 70% RH.

The result of an attack by micro-organisms is a loss of mass of the materials,which can lead to structural alterations which modify the functional properties,such as mechanical properties.In view of these results,three environments are chosen in this study to assess the durability of hemp aggregates used for vegetal concretes.The second one is an accelerated aging imposing variations in humidity.The relative humidity varies from 40% RH to 98% at a fixed temperature of 30 °C.Indeed,in the normal conditions of use of hemp concrete,unlike wood,hemp shiv should never be exposed to direct UV light or to liquid water.This temperature favours the development of microorganisms,which has been identified as a significant degradation factor.Finally,a harsher,outdoor aging process is used.The objective of this article is to identify the mechanism by which hemp shiv ages in the presence of moisture.The potential evolution of the functional properties of the material  is characterised and linked to the micro-structural changes  occurring in the different environments.The acoustic properties are measured using a Kundt tube.Two types of properties are obtained: the acoustic absorption co-efficient α and the transmission loss TL.The acoustic absorption co-efficient is the proportion of sound energy absorbed by a material.It is expressed for values ranging between 1  and 0.The transmission loss  represents the sound insulation provided by a material.3 measurements are taken for each batch of bulk shiv over a frequency range [250–2000 Hz].At A0,the batches contain 40.7 g of hemp shiv,to obtain a controlled density of 130 kg·m−3 in the volume of the sample chamber.The different batches are aged and reused for the acoustic measurements.The hydric behaviour is determined on the basis of the water vapour sorption isotherms using a DVS machine.A few granules representing a few tens of mg are suspended in a microbalance within a sealed thermostatically controlled chamber at 25 °C.The schedule for the DVS is set to start at 0% RH up to 95%.A given relative humidity is applied until the weight change of the sample is less than 0.0005%.min−1 or during 12 h if the weight is not stabilised.Sorption isotherms are produced by plotting mass change against relative humidity  and illustrate the water vapour sorption capacity as a function of the relative humidity.The overall sorption behaviour across the whole range of relative humidity values is simulated using the GAB model,as described in an earlier study.

Depending on the kind of porosity,it may be open and accessible for measurement,open but not accessible to measurement,or closed.With a pore size in the millimetre range,the interparticle porosity,represented in grey in Fig.3,is always open and accessible.On the other hand,the intraparticle porosity may contain closed pores and pores not accessible to the measurement.For simplicity’s sake,no distinction is drawn between intraparticle porosity which is closed or open but not accessible; both are denoted by Φintra_closed.This category is randomly represented in dark green in the diagram.The open and accessible intraparticle porosity is called Φintra_opened.By combining different techniques,it is possible to quantify the different volume fractions corresponding to the vegetal part or to each type of porosity.In all cases,these volume fractions are expressed as a function of a volume of bulk shiv.The bulk density ρ of the hemp shiv is the ratio of the mass of a batch of bulk hemp shiv to the volume it occupies in unstressed conditions.The density of the plant cell wall ρcell wall is an intrinsic value of the material,which depends on its chemical composition.In this case,the vegetal cell wall is expected not to contain any porosity.The volume corresponding to the vegetal cell walls of the material is measured by introducing a fluid into the pores in the material.Knowing the mass of the sample introduced,the density of the vegetal part can then be calculated.To measure this density,the hemp shiv is ground to a powder of grain size less than 500 μm in order to eliminate the porosities of the vegetal cell walls.The volume of the powder is then measured using a helium pycnometer.New energy storage systems have been continuously developed for replacement of fossil fuel to meet global energy requirements in the last decades.Multifunctional materials with an integration of structural and non-structural functions create new areas in the advanced energy storage system,such as structural super capacitor,which can maintain its capacitive function under a mechanical loading.At least two components of structural super capacitor are required to satisfy structural function such as structural electrode and structural electrolyte or separator.Maybe the structural electrolyte is more challenging,because that it must combine high ionic conductivity with good mechanical strength.However,it is generally known thationic conductivity and mechanical performance have an inverse relationship,because ionic conductivity requires pore structure for ion migration but strength needs compact structure.

A bicontinuous structure of electrolyte is designed to keep a good balance of performance,where one phase provides ionic conduction and the other phase is responsible for mechanical properties.The earliest structural electrolyte is polymer resin as structural component and ionic liquid based electrolyte as ionic conductive phase because polymer-based electrolyte has good mechanical properties,long lifetime,short charging time and wide potential window.Generally,polymer resin may contain of epoxy resin with more than two oxirane groups,polyethylene oxide or polyethylene glycon,while ionic liquid phase can combine several types of cations and anions.Shirshova et al.prepared ionic liquid-epoxy resin composites to obtain a structural electrolyte with ionic conductivity of 0.8 mS·cm−1 and a Young’s modulus of 0.2 GPa.Cole et al. reported polymer electrolyte-based stretchable super capacitors with a specific capacitance of 5–10 F·g−1 and mechanical stress of 0–3 MPa in suit microtensile characterization.Greenhalgh et al.fabricated structural super capacitors with epoxy which exhibited a compressive strength of 19.44 MPa and a specific capacitance of 4.5 m F·g−1.A novel structural super capacitor based on ionic liquid-polyester resin had a specific capacitance of 2.48 F·g−1,an equivalent series resistance Rs of 370 Ω and an in-plane shear strength of 102.4 MPa.However,the polymer electrolytes tend to have a low specific capacitance,and as the electrochemical property improves,the mechanical performance typically decreases,vice versa.Thus such polymer electrolyte may not well solve the challenge of balancing the electrochemical and mechanical properties of structural super capacitor.Recently,another kind of structural electrolytes were reported for building applications,cement as structural component and aqueous electrolyte as second phase.Normally cement as gel materials has high mechanical strength as well as prosperous pore structure.The pore size of pore structure can be divided into b20 nm,20–100 nm,100–200 nm and N200 nm,vertical grow rack and the amount of macropores in cement is N90% of total pores.As hydrated radius of aqueous electrolyte is generally smaller than 0.5 nm,such pore structure in cement is large enough to be filled with aqueous electrolyte to form structural electrolyte as well as to provide channels for ions passing,which is similar to the effect of pore size on the performance of electrodes.Zhang et al.reported a cement-based structural electrolyte with a specific capacitance of 10 F·g−1 and a compressive strength of 9.85 MPa.

Subsequently,Xu et al.fabricated a structural electrolyte based on geopolymer with a compressive strength of 33.85 MPa and a specific capacitance of 33.4 F·g−1.Ma et al.also reported a combining magnesium phosphate electrolyte with a compressive strength of 24.5 MPa and a specific capacitance of 40.9 F·g−1.Therefore,combining cement with aqueous electrolyte is a promising approach to develop structural electrolyte due to its low cost,structural integrity,chemical stability and good compatibility with structural component.Thus pore structure has an important role in the performance of cement-based structural electrolyte.The porosity and pore inter connectivity are likely to play critical roles in characterizing the pore structure of the structural electrolyte.Hemp fiber has been chosen to alter pore structure of cement based structural electrolyte in this work.There are two reasons for choosing the hemp fiber as pore forming agent.The first reason is that unique interconnected partially graphitic carbon nanosheets with significant volume fraction of mesoporosity has been created from hemp fiber,which exhibits excellent electrochemical performance in super capacitor and sodium ion battery.The other reason is that a large content of hemp fiber often leads to considerable number of macropores,which can result in forming interconnected pore structure in cement.Thus the effect of pore structure of structural electrolyte on the performance of structural super capacitor was investigated by adding various volume fractions of hemp fiber in this work.Typical SEM image of the structural electrolyte containing 15 vol% of hemp fiber is shown in Fig.3a and the corresponding EDX analysis result is listed in Fig.3d.It is clearly seen that hemp fiber is nonuniformly distributed in the matrix due to the large fiber content and non-homogeneous mix.Due to the presence of hemp fiber seriously interfering with image processing,careful selections of parts of SEM images without hemp fiber were used to measure the two parameters of pore structure,including porosity and pore connectivity,like Fig.3b.Image analysis technique is employed to process the SEM images to quantitatively characterize pore structure of the structural electrolyte with hemp fiber,like Fig.3c.

Hemp powder was also tested to investigate the regularity of the results and compare them with shiv

The wett ability of the surface is controlled by the surface chemical composition as well as by the morphology of the mic-structure.Surfaces with a similar chemical composition may have different wett ability behaviour due to the surface topology.In this study,the surface of hemp shiv underwent micro-structural changes via deposition of an organo-functionalised silica coating.Ethanol diluted sol series enhanced the surface roughness of the hemp shiv.At higher HDTMS loading,undiluted coatings  lowered the surface roughness of the shiv which could explain the reason for lower contact angles compared to diluted coatings.Sol A-1 and sol A-5 have HDTMS molecules that are not fully hydrolysed and being deposited onto the membrane as a flat thick film as seen in Fig.6b.The reduced surface roughness can be attributed to the extra HDTMS molecules on the coated surface.Since an organic-inorganic hybrid coating was used,the ratio of TEOS: HDTMS was critical to control the roughness of the coatings resulting in variable water repellent properties of the coated hemp shiv.Most of the coatings enhanced the surface roughness except sol A-1 and sol A-5.These coatings had smooth surfaces with cracks which could explain the lower contact angles even though it had the highest loading of hydrophobic agent.It was observed that the TEOS: HDTMS molar ratio in the coating formulations affected the hydrophobicity of the coated hemp shiv.From Fig.3 it can be seen that varying the concentration of HDTMS in the formulations affects the water contact angle.When TEOS: HDTMS was 1: 0.01 corresponding to 0.5 wt% HDTMS,the contact angle was below 100◦ which suggests the concentration of the hydrophobic agent was too low to provide sufficient level of hydrophobicity.

The best results were obtained with TEOS: HDTMS ratio 1: 0.02  with contact angles up to 118◦.However,when the TEOS: HDTMS ratio was increased to 1: 0.06,the hydrophobicity was decreased for the undiluted sol coatings.These results can be explained by the combined effect of surface roughness and energy.TEOS is hydrophilic whereas HDTMS is hydrophobic and changing their molar ratio can affect the surface roughness and energy ofthe coated material.Increasing the HDTMS concentration would reduce the surface energy.However,best trimming trays the surface roughness can be reduced if the HDTMS concentration is high enough as the extra silane fills the inter-particle gap.Similar results have been reported in different coating systems.Although sol B-7 coating enhanced the surface roughness,it had developed cracks which lowered the water contact angle to 98◦.The presence of surface cracks arising as a result of shrinkage after drying the coated shiv is a significant factor to be considered when hydrophobic properties are concerned.The hydrophobicity of modified hemp shiv can be compromised as the water molecules can penetrate through the cracked coating wetting the bulk of the material over time.Therefore,sol-gel coatings chemically modified the surface of hemp shiv which overall improved the hydrophobicity of the material.The high water repellence can be attributed to the long alkyl chains of HDTMS that provide high hydrophobicity.The chemical composition of hemp shiv is mainly composed of cellulose,hemicellulose and lignin,which altogether contain a large percentage of oxidized carbon in their structure.Hydroxyl groups are known to contribute towards majority of the carbon-oxygen bonds in bio-based materials.The XPS data confirmed that the sol-gel deposition on hemp shiv significantly altered the surface chemistry.The surface carbon content of the coated hemp shiv decreased by 41.28%.On the other hand,the oxygen content increased by 26.51%.

This change in C/O ratio and increase in surface oxygen concentration can be attributed to O CH3 bonds present in the polysiloxane coating on the surface of the sol-gel coated hemp shiv.Moreover,the decrease in the surface carbon concentration of the sol-gel coated shiv can be attributed to the masking effect of the polysiloxane coating which reduces the detectability of surface cellulose and hemicellulose.The C1s high resolution XPS spectra indicate that the surface has been modified by the silica based coating that led to disappearance of C3 and C4 components of the C1s peaks.A shift in the binding energy of C2 component  was observed along with the decrease in the intensity ofthe C2 componentfor the sol-gel coated sample.This shift indicates the presence of a carbon atom linked to an oxygen and silicon atom.It has also been shown that curing above room temperature drives the dehydration reaction at the adsorption sites between hydroxyl groups of the cellulose and the silanols forming Si O C bonds.These bonds are formed by the linkage between polysilanol network with the cellulose hydroxyl groups via polycondensation as illustrated in Fig.9.The increase in the intensity of C1 component for sol-gel coated sample from 48.01% to 91.09% indicates the presence of C H and C C bonds from the HDTMS hydrocarbon chain.Hemp concretes are the most widely used biobased concretes in France.As an example,VICAT,one of the European leaders in the production of building materials,has developed a construction system composed of hemp shiv and Natural Prompt Cement.Although construction rules exist for these materials,their growth is still limited by the lack of knowledge and high variability of the performances of biobased concretes,especially for their mechanical properties.In addition,even if it is not the main performance expected,they still require sufficient mechanical resistance to be unmolded,transported onsite,and handled.Several parameters,such as setting delays of the binder or potential degradation of plant particles have been identified to explain their mechanical weakness.

Moreover,on existing buildings,problems of powdering of the materials in the core have been observed even when using binder/vegetal couples validated by the construction rules.Currently,while cementitious binders are well characterized,the physico-chemical mechanisms that affect the setting of the binder in biobased concretes have not yet been well understood so far.The modification of the hydration of the binder is related to the extraction of compounds from the plant aggregates which are not chemically inert,contrary to the mineral aggregates of conventional concretes.As a consequence,empirical testing is currently used to assess the compatibility of specific biomass particles and binders couples.These tests validate the performance of a biomass batch and binder couple at a given time,but do not consider the important variability of plant chemical composition and micro-structure.The latter depends for example on plant species,genetic material  and environment of its growth,but also on their transformation process.This lack of knowledge about the robustness and performance of plant-based concretes is the main obstacle to their development.Hemp crete offers a means of achieving the rules set by the French national environmental regulations,which applies since 2022,but also of improving technical aspects of the concrete used in construction today.When dry,hemp has a very low bulk density of around 110 kg.m− 3,meaning that hemp-based concrete is lightweight.It is an effective insulation material with good hygrothermal and acoustic properties.It has low thermal conductivity  due to its porosity and low density.That porosity and the hydrophilicity of hemp create a buffering effect that regulates the humidity within the concrete.Hemp crete is also interesting from an ecological point of view,as it requires no pesticides and cleans the soil,leaving it in a better state than before.Furthermore,it reduces the distance and time of transport from the source to the building site since it uses materials cultivated locally.Finally,the plant particles in the hemp concrete act as a CO2 trap during the lifetime of a building.

Existing studies on bio-based concretes formulated with mineral binders and vegetal aggregates from different origins and chemical compositions showed that the properties of materials are disparate.As an example,for identical formulations,the use of nine types of hemp shiv from different sources leads to differences in compression strength by a factor of 5,while the impact on thermal conductivity is smaller.These results are attributed to the particle size distribution of the bio-resources,their water absorption and chemical composition and to the lixiviation of vegetal compounds.About impact of vegetal components on the hydration of binders,some studies highlight the modification of the mechanisms and kinetics of hydration of mineral binders by vegetal components.Indeed,during the processing of plant-based concretes,vegetal compounds,such as polysaccharides and polyphenols extracted in the fresh concrete mixture,interact with the mineral phases.Some of these extracted compounds can slow down or even completely inhibit the setting of the binders.These results,observed with various vegetal concrete formulations containing wood,hemp,miscanthus,corn or sunflower,depend on the selected plant-mineral binder couple.A correlation can be drawn between the biochemical nature of raw plant materials,including the plant cell wall quality,the composition of the leachates,and the mechanical properties of bio-based concretes.On a different scale of analysis,an interfacial transition zone  is observed around the vegetal particles.The ITZ is a gradual transition region where the composition and micro-structure of the binder matrix are affected by the presence of the aggregate particles.This impacts on the physical properties,mechanical properties,functional properties  and durability  of vegetal concretes.In this study,a newly implemented protocol is set up using a hemp pellet put into a cement paste.The halo of less hydrated material created around this pellet is monitored using image analysis.Different analysis methods  have been used to characterize the hemp crushed for the pellet and to analyze the ITZ and the hydrated matrix.The cement used to make up the cement paste is a Portland cement CEM I 52.2 R,trimming tray kept at a temperature of 20 ◦C in a sealed plastic bag.To reduce bleeding in the cement paste,KELCO-CRETE DG-F from BASF  was used.This is a water-soluble biopolymer used in hydraulic cementious systems as a viscosity modifying agent.The characterizations of hemp were performed on sample dried at 50 ◦C for at least 2 days,in accordance with the RILEM recommendations.The hemp used for the experiments has a bulk density of 116 kg.m− 3.Its particle size distribution is extremely heterogeneous and the initial rate of absorption  is 135 %.

A ThermoFisher Scientific iS50 device with Attenuated Total Reflection  mode was used for Fourier transform infrared spectroscopy measurements.The spectra were acquired from 500 to 4000 cm− 1,with a digital step of 0.5 cm− 1  and on average,with 32 successive scans.Spectra were corrected between 1900 and 2400 cm− 1 to remove CO2 contribution,with an automatic baseline.The data were processed using OMNIC® software.It was decided to differentiate the internal face  from the external face  of the shiv to see its influence.X-ray diffraction  analysis was performed on a Brüker D8 Advance device directly on a pellet of constant size,which was made of 0.1 g of hemp ground and compressed at a pressure of 10 tons.After drying at 50 ◦C,the pellet was removed from the oven and tested as soon as possible  to reduce the impact of water absorption due to air exposure,which can affect the results.The data were analyzed using Specta Software.In order to study the ITZ between the hemp and the binder,the experiments were conducted on hemp pellets in contact with cement paste.The protocol was adapted and improved to tackle the issues encountered in previous studies like robustness,repeatability and accuracy,to monitor the formation of the ITZ from the moment the binder is finished being poured.The compositions of the cement pastes used in this study are presented in Table 1.The overnight data acquisition showed the formation of the ITZ.First,the pellet absorbs the water in the cement paste.Then it begins to dry,and the ITZ forms from its outer edges after approximately 5 h.The cement paste slowly becomes lighter in the vicinity of the pellet.The extracts of hemp seem to be released as soon as the pellet is placed into the cement paste,and percolate around the pellet over a distance of few millimeters.Then,the paste begins to set from the edges of the mold to the pellet,and the halo appears due to the presence of chemical components which delay or interfere with the setting.FTIR spectra of cement  show that while similarities can be found between the ITZ and the hydrated matrix in terms of the micro-structural composition,like the presence of portlandite and O–H bending in cement hydrates,certain components are also in common with the anhydrous cement,like the presence of gypsum,alite,belite,and anhydrite.FTIR mapping shows the evolution of the area under the band relative to portlandite at 3640 cm− 1,with a base line from 3660 to 3600 cm− 1.Portlandite is chosen because it partially reflects the hydration of the cement.The color scale of the mapping ranges from blue,showing a very small vibration band area,through green,to red,highlighting a larger vibration band area.The lower part of the map corresponds to the area near the hemp pellet,as evidenced by the observation.

The mineral element content in hemp seeds is nutritionally interesting

In order to monitor the effects of reformulation and heating treatment on the lipid oxidation of beef burgers, lipid oxidation was measured in all samples, before and after cooking.Significant differences  were obtained with the addition of GEs, in both raw and cooked samples.In raw samples, burgers reformulated with chia oil  registered higher TBARS values  than the control sample, being burgers with the highest replacement level  which showed the highest  TBARs values.In fact, BCh50 samples showed 3.5 times more oxidation than the control sample.Burgers reformulated with GE with hemp oil  showed similar TBARs values   than control.This fact was in concordance with several authors who reported that the use of GE elaborated with vegetable oils as animal fat replacement in meat products might be complex due to the high oxidation susceptibility of these unsaturated oils.The differences in the lipid profile of the oils, the content of polyunsaturated fatty acids, and the temperature used to generate oleogels or gelled emulsions could affect the MDA levels.It must be noticed that TBARS values in burgers reformulated with GE elaborated with amaranth flour and hemp oil  as well as the burgers reformulated  with GE elaborated chia oil  were below the malonaldehyde limit for acceptability reported by Trindade, Mancini-Filho, and Villavicencio   for loss of sensory attributes and perception of oxidation by consumers.However, it is important to highlight that cooked burgers reformulated with GE elaborated with amaranth flour and chia oil showed values above the threshold limit for consumer acceptability.The influence of the addition of GEs on sensory attributes of raw beef burgers is shown in Table 8.Relevant parameters affecting consumer purchase were measured, such as “color”, “rancid aroma” and “product appearance”.

Panelists did not detect differences between control and reformulated burgers  for any of the three evaluated parameters.This result agreed with the instrumental color parameters,hydroponic grow tent where L*, b* and h* values had no differences  between samples and the rest of color parameters  showed small differences which were statistically significant but without practical significance.In the case of cooked samples, juiciness, chewiness, fat sensation, graininess and general acceptability were evaluated.The only attribute that showed differences  between samples was graininess: BCh25 and BH25 showed the highest  score  without statistical differences between them , while control sample had the lowest.These results agreed with the instrumental analysis since textural analysis revealed only differences in cohesiveness between some samples.For the preference test, control sample  and BH50  were the most chosen.It has to be mentioned that the information about the nutritional improvement  achieved in reformulated burgers was not communicated to panellists and that could be relevant and affect their sensory attractiveness.Hemp  is a widespread herbaceous plant native from Central Asia that belongs to the Cannabaceae family.This plant could be considered as one of the first crops because it is thought that it was cultivated in China 8500 years ago.Hemp has been traditionally cultivated with industrial, medicinal and food purposes.Its fibre was obtained from stems, specifically from the phloem, and it has been widely used, especially in the shipbuilding industry.Female flowers were useful because of their pharmacological properties, and seeds were used mainly as food.Hemp phytochemistry is quite complex and cannabinoids are its most distinctive compounds.They are produced almost entirely in glandular trichomes, which are commonly located in the bracts of female flowers.Nevertheless, other parts of the plant, such as seeds, could contain a small quantity of cannabinoids , which is subject of regulation in different countries of the world.

The most important one is Δ9 -tetrahydrocannabinol , due to its psychoactive properties, and only varieties with low Δ9 -THC content can be cultivated.Nowadays, the consumption of hemp seeds and derivative products is increasing.Whole hemp seeds are used as a raw material, but could be consumed as food as well, and hulled hemp seeds are commonly marketed as functional food.Hemp seeds contain large amounts of fibre, fat, and protein, at 27–40, 25–35, and 18–28 g/100 g, respectively.They contain significant amounts of linoleic acid, which represents 50% of total fatty acids, 16–19% of α-linolenic acid, 12–17% of oleic acid, and other minor fatty acids, being remarkable the presence of γ-linolenic acid.In addition to nutrients, hemp seeds contain bio-active compounds which confer a biological potential, such as antioxidant, antimicrobial and cytotoxic properties.Chen et al. attribute some of these bio-active properties to phenolic compounds, the main being lignanamides, such as cannabisins.The studies about mineral elements in hemp seeds are scarce, but Callaway  and Mihoc et al. reported an interesting content of some of them, such as phosphorus, potassium, magnesium, calcium, iron, zinc, manganese, and copper, which are essential dietary elements for mammals and are involved in many physiological processes.Mineral element bioavailability could be compromised by different anti-nutrient components in foods, such as phytates and oxalates, which are present in hemp seeds.Phytic acid is the main storage form of phosphorus in seeds and it can form insoluble complexes with some cations, such as calcium, magnesium, iron, and zinc.The chelating capacity of phytates is especially damaging in the case of iron and zinc, and their deficiencies constitute a significant public health problem.The absorption of calcium of plant origin is impaired by the presence of oxalic acid, which promotes the formation of insoluble calcium oxalates.The objectives of this study were to determine the mineral element content of different varieties of whole hemp seeds and commercial hulled hemp seeds, as well as the phytate content, which is closely related to the mineral element bio-accessibility.Phytates were determined by an indirect iron  complexometry with sulfosalicylic acid like an indicator of the titration endpoint, according to RomeroAguilera et al..The extraction was carried out under magnetic agitation for 90 min from 2 g of sample with 40 ml of HCl 0.4 M, which contained Na2SO4 5%.

The resulting suspension was centrifuged at 1890g during 8 min, and the supernatant was filtered and made up to 50 ml with the extraction solution.After that, 20 ml of the extraction solution, 20 ml of FeCl3 0.02 M , and 20 ml of sulfosalicylic acid 20%  were added to 25 ml of the extract, and the mixture was made up to 100 ml with distilled water.Blank was prepared in the same way, but 25 ml of the extraction solution were used instead of the extract.The solutions were heated for 15 min in a boiling water bath and then they were cooled in an ice bath.One aliquot of 20 ml was pipetted together with 200 ml of distilled water and 1.5 g of glycine were added.This solution was heated at 70 ◦C and titrated with EDTA 10 mM while still warm until the solution turned yellow.All the volumes obtained from the titration of the samples and standards were subtracted from the blank value, obtaining the amount of EDTA equivalent to the complexing activity of.the phytates in the sample.For quantification purposes, a calibration curve was built using a commercial phytic acid standard.The analyses were performed in triplicate and the results were expressed as g of phytic acid equivalents /100 g.The results of mineral element analysis of both whole and hulled hemp seeds are shown in Table 2.Regarding macroelements, sodium was the least abundant, with an average value of 2.75 and 1.41 mg/100 g in whole and hulled hemp seeds, respectively.All the samples contained less than 5 mg/100 g.On the other hand, phosphorus was most abundant one, with an average value of 871.2 and 1099.5 mg/100 g in whole and hulled hemp seeds, respectively.Phosphorus content was lower in whole hemp seeds, being the maximum value 928.1 mg/100 g, which corresponded to ‘Tiborszallasi’ variety.Potassium content was also high in hemp seeds, especially in hulled seeds, which contained on average 919.5 mg/100 g, while the average content in whole hemp seeds was 569.6 mg/100 g.Potassium ranges were wide, from 311.5 to 713.6 mg/100 g in whole hemp seeds and from 778.8 to 1067.7 mg/100 g in hulled hemp seeds.Magnesium content was also higher in hulled hemp seeds, in which ranged from 482.3 to 934.2 mg/100 g, with an average value of 696.9 mg/100 g.However, cheap grow tents the range in whole hemp seeds was very narrow and there were not statistically significant differences between the eight analysed varieties.The average magnesium content in whole hemp seeds was 383.4 mg/100 g.Calcium content, on the contrary, was higher in whole seeds, with an average value of 175.6 mg/100 g, being half in hulled hemp seeds.

In respect to microelements, most of them were more abundant in whole seeds.Iron was the major microelement in whole hemp seeds, with an average content of 8.04 mg/100 g, closely followed by zinc and manganese, whose average contents were 7.94 and 7.48 mg/100 g, respectively.Zinc was the most abundant microelement in hulled hemp seeds, with an average content of 9.81 mg/100 g.Iron content in hulled hemp seeds were slightly lower than in whole seeds, 7.83 mg/100 g, while manganese content was much lower, 5.18 mg/100 g.Copper content was lower than the other microelements, on average, 2.30 and 1.48 mg/100 g in whole and hulled hemp seeds, respectively.Among the analysed varieties, ‘Carmagnola’ variety stood out because it had the maximum values of sodium, calcium, manganese, iron, and zinc, and the minimum values of magnesium and phosphorus, and the ‘Kompolti’ variety stood out because it had the maximum values of potassium and copper, and the minimum values of calcium, manganese, and iron.Regarding hulled hemp seeds, there were a wide variation among the different brands.As it has been said previously, few studies on mineral elements in whole hemp seeds are available, so it is difficult to compare these results with previous studies.Callaway  reported the contents of mineral elements of the ‘Finola’ variety, which was not analysed in this study, and Mihoc et al. studied five different Romanian varieties that were not analysed in this work either.The sodium content reported by Callaway  was slightly higher, 12 mg/100 g, while all the varieties analysed in this work had sodium content lower than 5 mg/100 g , but its content was much lower than the other macroelements in both cases.That study also reported higher potassium content , closer to hulled hemp seeds than to whole seeds.Mihoc et al. obtained a wide range for this mineral element, from 569.3 to 1889.7 mg/100 g, on average.Two of those varieties had potassiumcontents within the range of this study , but the other three had much higher content.Calcium values reported by Mihoc et al. were close to those of this work , except one of the varieties, which had a content three times higher than the maximum value.The magnesium content range reported by Mihoc et al. included all the values obtained in this work, and Callaway  indicated a higher value, 483 mg/100 g, but close to the maximum obtained in this work.According to Callaway , phosphorus was the most abundant mineral element, but the value was higher, 1160 mg/100 g, closer to phosphorus content in hulled hemp seeds, which were higher than 1000 mg/100 g in every sample.Iron content reported by Callaway  was slightly higher than those of this work, 14 mg/100 g, but the values reported by Mihoc et al. were higher than 160 mg/100 g, 20 times the average value in whole hemp seeds.Manganese, copper, and zinc content data were consistent to those reported by Callaway  and Mihoc et al..

The only literature source of mineral element content data in hulled hemp seeds is the FoodData Central.Sodium, magnesium, calcium, iron, manganese, copper, and zinc values included in the database were close to those of this work, while potassium and phosphorus values, 1200 and 1650 mg/100 g, respectively, were higher than the maximum values obtained in this work.Considering the nutrient reference values  of mineral elements established by the European Union , Fig.1a represents the percentage that 100 g of whole and hulled hemp seeds contribute to those NRVs, while Fig.1b represents the contribution percentages of 30 g, which is the serving size.As it can be seen in Fig.1a, and according to European Union regulation on nutritional claims made in foods, both whole and hulled hemp seeds could be considered high in magnesium, phosphorus, manganese, copper, and zinc because their contributions were higher than 30% of NRVs.The contribution of whole hemp seeds to potassium NRV was slightly lower than 30%, so they could be considered as a source of potassium , while hulled hemp seeds could be considered, high in potassium.Whole, but not hulled hemp seeds, could be considered a source of calcium.