Influence of Calcination on the Physical Characteristics and Nitrogen Removal Performance of Clinoptilolites

The influences of roasting activation on the particle morphology, microscopic structure, and adsorption properties of natural clinoptilolites were investigated. The experimental results show that the optimal modified conditions include a calcination temperature at 400 ℃, a roasting time of 0.5 h, and furnace cooling. The ammonia nitrogen removal rate from analog renewable water of the modified clinoptilolites reached 72% in the optimized conditions, which is 12% higher than that of natural ones. Scanning electron microscopy analysis showed that the surface morphology changed, the micro-hole size increased, and the surface became smoother and more uniform after calcination. The single-point total adsorption average pore width increased from 7.74 nm to 10.64 nm.

Safety and efficacy of purified clinoptilolite-tuff treatment in patients with irritable bowel syndrome with diarrhea:Randomized controlled trial

BACKGROUND Irritable bowel syndrome(IBS)is a highly prevalent gastrointestinal disorder with poor response to treatment.IBS with predominant diarrhea(IBS-D)is accompanied by abdominal pain as well as high stool frequency and urgency.Purified clinoptilolite-tuff(PCT),which is approved by the Food and Drug Administration for use as a dietary supplement with the brand name G-PUR®,has previously shown therapeutic potential in other indications based on its physical adsorption capacity.AIM To assess whether symptoms of IBS-D can be ameliorated by oral treatment with PCT.METHODS In this randomized,placebo-controlled,double-blind pilot study,30 patients with IBS-D diagnosis based on Rome IV criteria were enrolled.Following a 4-wk run-in phase,14 patients were randomized to receive a 12-wk treatment with G-PUR®(2 g three times daily),and 16 patients received placebo.The relief from IBS-D symptoms as measured by the proportion of responders according to the Subject’s Global Assessment(SGA)of Relief was assessed as the primary outcome.For the secondary outcomes,validated IBS-D associated symptom questionnaires,exploratory biomarkers and microbiome data were collected.RESULTS The proportions of SGA of Relief responders after 12 wk were comparable in both groups,namely 21%in the G-PUR®group and 25%in the placebo group.After 4 wk of treatment,36%of patients in the G-PUR®group vs 0%in the placebo group reported complete or considerable relief.An improvement in daily abdominal pain was noted in 94%vs 83%(P=0.0353),and the median number of days with diarrhea per week decreased by 2.4 d vs 0.3 d in the G-PUR®and placebo groups,respectively.Positive trends were observed for 50%of responders in the Bristol Stool Form Scale.Positive trends were also noted for combined abdominal pain and stool consistency response and the Perceived Stress Questionnaire score.Only 64%in the G-PUR®group compared to 86%in the placebo group required rescue medication intake during the study.Stool microbiome studies showed a minor increase in diversity in the G-PUR®group but not in the placebo group.No PCT-related serious adverse events were reported.CONCLUSION In this randomized,double-blind,placebo-controlled study,the PCT product,G-PUR®,demonstrated safety and clinical benefit towards some symptoms of IBS-D,representing a promising novel treatment option for these patients.

Influence of Intercropping Maize with Cowpea and Fertilization with Clinoptilolite on Forage Yield and Quality

Maize forage is poor in protein content which leads to low quality and nutritive value.Regarding the high feed costs of protein supplementations,legumes can be used in livestock nutrition for their high protein content,and thus,provide cost savings.In this study,maize(Zea mays L.)and cowpea(Vigna unguiculata L.)were intercropped in different sowing densities and fertilization with clinoptilolite and their monocropping equivalents were tested to determine the best intercropping system on forage yield and quality.Maize was cultivated alone(75,000 plants·ha^-1)and intercropped with cowpea as follows:75,000 plants·ha-1 of maize and 37,500 plants·ha^-1 of cowpea(MC1),75,000 plants·ha^-1 of maize and 50,000 plants·ha-1 of cowpea(MC2)and 75,000 plants·ha^-1 of maize and 75,000 plants·ha^-1 of cowpea(MC3),in rows alternating with maize.The highest dry matter yield was produced by MC3(23.8 t·ha^-1),and the lowest by SM(20.7 t·ha^-1)in fertilization with clinoptilolite.All intercropped systems had higher crude protein contents,MC1(101 g·kg^-1 DM),MC2(108 g·kg^-1 DM)and MC3(117 g·kg^-1 DM),than the monocrop maize(84 g·kg^-1 DM)in fertilization with clinoptilolite.Intercropping of maize with cowpea and fertilization with clinoptilolite reduced neutral detergent fiber,resulting in increased forage digestibility.Therefore,maize intercropping with cowpea and fertilization with clinoptilolite could substantially increase forage quantity and quality,and decrease requirements for protein supplements as compared with maize monocrop.

Photocatalytic Degradation of Ethylene Dichloride in Water Using Nano TiO₂Supported on Clinoptilolite as a Photocatalyst

In this article one of the advanced oxidation processes (AOP) combined methods, photocatalyst /H2O2, is utilized in order to study photodegradation of ethylene dichloride (EDC) in water. Nano Titanium (IV) Oxide, supported on Clinoptilolite (CP) (Iranian natural zeolite) using solid-state dispersion (SSD) method for improvement of its photocatalytic properties. The results show that the TiO2/Clinoptilolite (SSD) is an active photocatalyst. The effects of five important photocatalytic reaction parameters including the initial concentration of ethylene dichloride, the ratio of TiO2/Clinoptilolite, the catalyst concentration, H2O2 concentration and pH in photodegradation of ethylene dichloride were examined. In this experiments, the design and also the optimum parameters were obtained by Taguchi Method, using Design Expert8®software. Taguchi's L27 (5^3) orthogonal array design was employed for the experimental plan. Four parameters were found to be significant whereas, pH was found to be an insignificant parameter after conducting experiments. A first order reaction with K = 0.007 min-1 was observed for the photocatalytic degradation reaction.

Removal of Ag(I) from Aqueous Solution by Japanese Natural Clinoptilolite

The present study examined the adsorption of silver ion in aqueous solution onto natural clinoptilolite zeolite from Futatsui Mine, Akita Prefecture, Japan. The effects of various parameters, i.e., solution pH, adsorbent dosage, adsorption time, silver ion solution concentration, and temperature, on silver ion adsorption process onto clinoptilolite were examined. Additionally, the thermodynamics of the silver ion adsorption process was investigated. The optimum pH for silver adsorption was determined to be around 4.0. The adsorption process could be well described by the Langmuir isotherm model. The calculated maximum adsorption capacity was 0.64 mmol/g. Adsorption kinetics studies were also conducted. The results showed that the adsorption process preferentially followed the pseudo-second-order kinetics model over the pseudo-first-order model. Furthermore, with decreasing aqueous solution temperatures, the adsorption kinetics became slower and the amount of silver ion adsorbed increased. The thermodynamic values, ΔG0, ΔH0, and ΔS0, indicated that adsorption was an exo-thermic and spontaneous process.

Enhanced nitrification in integrated floating fixed-film activated sludge (IFFAS) system using novel clinoptilolite composite carrier

The integrated floating fixed-film activated sludge (IFFAS) process is an ideal preference for nitrification attributing to the longer sludge age for nitrifiers. However, as the core of this process, conventional carriers made of polymer materials usually exhibit negative charge and hydrophobicity on the surface, which is unbeneficial to nitrifying biofilm formation. In this study, novel clinoptilolite composite carriers with favorable hydrophilicity, positive charge and nitrification-enhancing capability were made and implemented in IFFAS system. In comparison with conventional carriers, the novel clinoptilolite composite carriers displayed positive charges on the surface (11.7±1.1 mV, pH 7.0) with increased hydrophilicity (surface contact angle dropped to 76.7°). The novel-carriers-based reactors achieved significantly better NH4+-N removal efficiency at different influent concentrations, dissolved oxygen (DO) levels and shock loads (NH4+-N removal efficiency rose up to 20% comparing with the control reactors filled with polyethylene (PE) carriers or activated sludge). High-throughput sequencing (HTS) results indicated the novel clinoptilolite composite carriers provided favorable niche for more types of bacteria, especially for Nitrosomonadales and Nitrospirales (the functional nitrifiers in the system). The population of Nitrospirales increased by 4.51% by using novel clinoptilolite composite carriers comparing with using PE carriers, which ensured enhanced nitrification process. This study was expected to provide a practical option for enhancing wastewater nitrification performance with the novel clinoptilolite composite carrier.

Propylsulfonic acid functionalized nanozeolite clinoptilolite as heterogeneous catalyst for the synthesis of quinoxaline derivatives

In this work,the natural nanozeolite clinoptilolite（Nano CP） was successfully functionalized by propylsulfonic acid and applied as efficient heterogeneous catalyst for the synthesis of quinoxaline derivatives in aqueous media.The nanocatalyst was characterized by various techniques such as CHN,XRD,FT-IR,BET,TGA/DTA,SEM,TEM and TEM-EDS.The results show its applicability as green,reusable and promising catalyst in organic synthesis.It was found that the nanocatalysts could be recycled and reused eight times without significant loss of catalytic activities.

Hydration Characteristics and Mechanical Properties of Cement-Based Materials Modified by Calcined Zeolite and Montmorillonite

Montmorillonite and clinoptilolite zeolite were used as representative materials to prepare calcined clay-cement binary cementitious materials in order to study the effect of calcination treatment on the activation of clay minerals and the activity difference between layered and framed clays in this research.The influence of different calcined clay content(2%,4%,6%,8%,10%)on the fluidity,compressive strength,microstructure,phase change,and hydration heat of cement-based materials were analyzed.The calcined clay improves the fluidity of cement-based materials as compared with the uncalcined group.The addition of calcined montmorillonite(CMT)improves the development of mechanical strength,and the optimal compressive strength reaches 85 MPa at 28 days with 8%CMT.However,the activity of calcined clinoptilolite zeolite(CZL)is weak with few reaction sites,which slightly reduced the mechanical strength as compared to the blank sample.The addition of CMT changes the microscopic morphology of hydration products such as C-S-H and C-A-H,leading to the formation and transformation of ettringite in the early stage.It promotes the gradual polymerization of Si-O bonds into Si-O-Si bonds simultaneously,which accelerates the early hydration process.However,CZL acts mainly as a filling function in the cementitious system.In brief,CMT as an admixture can improve the mechanical properties of cement,but CZL has little effect.This work provides a guideline for the applications of calcined clay in cement,considering the influence of clay type on workability and mechanical strength.

Clays as dietary supplements for swine:A review

Clays are crystalline, hydrated aluminosilicate molecules composed of alkali and alkaline earth cations along with small amounts of various other elements. The best-known are montmorillonite, smectite, illite, kaolinite, biotite and clinoptilolite. The molecules in these clays are arranged in three-dimensional structures creating internal voids and channels capable of trapping a wide variety of molecules. As a result of this structure, clay minerals are regarded as a simple and effective tool for the prevention of the negative effects of many toxic compounds. Dietary supplementation with clays has been shown to improve weight gain and feed conversion in pigs. Where improvements in performance have been noted, one of the most likely explanations for the improvement is the fact clays increase nutrient digestibility. Clays reduce the speed of passage of feed along the digestive tract which allows more time for digestion. Feeding clays also causes morphological changes in the intestina mucosa such as an increase in villus height and an increase in the villus height to crypt depth ratio. These changes increase the surface area of the gastrointestinal tract thus increasing nutrient digestibility, Several studies have indicated that feeding clay reduces the incidence, severity and duration of diarrhea in pigs. The mechanism for the reduction in diarrhea is likely due to increases in the numbers of Bifidobacteria and Lactobacillus and decreases in Clostridia and E. coil in the small intestine of pigs fed clays. In addition, the numbers of pigs born alive and weaned, birth weight and weaning weight have been shown to be higher for sows fed clays. Several studies have indicated that clays can help mitigate the effects of mycotoxins. The aim of the present review is to focus on the various clays which have been given attention in recent research and to discuss their potential to improve pig performance.

Efficacy of Detoxsan~? powder on diarrhea caused by gastrointestinal neuroendocrine tumors

BACKGROUND Patients with neuroendocrine tumors(NETs) of the gastrointestinal tract suffer frequently from chronic diarrhea. A well characterized medical advice containing zeolite(Detoxsan~? powder) was applied to patients suffered from therapyrefractory diarrhea either by its frequency or by watery stool, despite receiving standard pharmacotherapy according to the guidelines for carcinoid syndrome and comorbidities. Detoxsan~? powder acts as an adsorbent and might reduce significantly symptoms of diarrhea in patients suffering from NETs.AIM To overcome the therapy-refractory diarrhea of patients with NETs by the zeolite containing medical advice Detoxsan~? powder.METHODS A total of 20 patients(12 female and 8 male) suffering from diarrhea either by its frequency or from watery stool caused by NETs were included. In each patient,the diagnosis had been confirmed by histology and somatostatin receptors expression proven by positron emission tomography/computed tomography using Ga-68-labeled somatostatin analogs. All patients received standard-of-care pharmacotherapy and were additionally given Detoxsan~? powder as an extemporaneous drug containing 90% natural Cuban zeolite and 10% magnesium aspartate. Recommended daily dosage ranges between 3 g once to three times per day. Each day dose and bowel movements were documented by the patients themselves in a pre-defined table. Additionally to the bowel movements quantitative determinations of serotonin, urea, creatinine and single ions were performed within the serum of the patients by commercially available equipment used as a matter of routine in the clinic.RESULTS All patients enrolled in this pilot study did not only suffer from NETs, but also from comorbidities and treatment-resistant diarrhea. There was insufficient control of diarrhea, most probably due to the secretion of hormones like serotonin produced by the slowly growing and highly differentiated NETs. All patients only took Detoxsan~? powder as an antidiarrheal drug. In general,response effects need several days to become perceptible and require an intake of Detoxsan~? powder for an extended time period or intermittently, if persisting stabilization of bowel movements could not be achieved. A correlation between NET grade, part and size of bowel resection and functionality of the tumor could not be demonstrated. A correlation between NET grade, part and size of bowel resection and functionality of the tumor could not be demonstrated. Therefore,diarrhea seemed to be based on the metabolic activity of the well-differentiated NETs, which eventually led to treatment resistance. In summary, 14 out of the 20 patients(70%) declared to be very content with using Detoxsan~? powder and observed a significant reduction of diarrhea, while the effective dose and intake period that resulted in a symptom relief varied individually.CONCLUSION Detoxsan~? powder is able to reduce significantly symptoms of NET-related diarrhea in the majority of patients. The duration of taking Detoxsan~? powder and its dosage vary individually.

Effect of Copper and Iron on Acidogenic Biomass in an Anaerobic Packed Bed Reactor

The aim of this study was to evaluate the effect of copper and iron on acidogenic biomass immobilized on clinoptilolite in an anaerobic packed bed reactor. Copper and iron were fed to the reactor at concentrations of 100 and 300 mg&middotL-1, respectively. Both metal ions had insignificant inhibitory effect over the metabolism of the biomass, specifically, on substrate consumption and production of volatile fatty acids (VFAs). The microstructural characterization of the biofilm by Scanning Electron Microscopy showed no effect on the morphology of the microorganisms after the metals treatment. Copper and iron removal was also measured in the reactor, achieving a breakthrough time of 3 days, during which removal efficiencies were higher than 90%. It was also observed that the biomass had a greater affinity for copper. The results indicate that acidogenic biomass can be used effectively as a sorbent agent. The pollution of river-streams with heavy metals—mainly copper and iron—was one of the most compelling motivations for conducting this investigation. The San Pedro River Basin, a trans-boundary river that originates near the mining town of Cananea, Sonora, México, and flows to Arizona, USA, exemplifies this environmental issue.

Tailoring Natural Zeolites by Acid Treatments

In this study, a comparison of a variety of existing acid treatment methods for zeolite based on their abilities to modify physical properties of the particles is performed. Evaluation of the effects that four different acids have on numerous properties of the zeolites including surface area, pore size, pore volume, thermal stability, IR spectra, crystallinity, and morphology is conducted and compared with the reference untreated zeolite. Furthermore, all five zeolite particles are evaluated for their adsorption properties in column mode experiments. The importance of the examined features is discussed. The results obtained in this work are compared to similar studies to examine which conditions greatly influence the zeolite modifications.

Alleviation of Pesticide Residue in Surface Water

Reduction of environmental pollution incurred from pesticide use is very important. Zeolite is a natural mineral capable of removing certain chemical contaminants from water. This study was carried out to test the effect of zeolite treatment on pesticide residue alleviation in surface water. Ten surface water samples were treated with natural zeolite by filtering through. An EPA method was used to extract pesticide residue from the water samples and the surfactant used to modify the net charge on the zeolite was hexadecyltrimethylammonium chloride (HDTMA-Cl). Gas chromatography-mass spectrometry was used to analyze water samples. Alleviation was achieved in all the 10 water samples that were filtered through zeolite. The highest removal of pesticides from water with zeolite included 100% of bifenthrin in sample CLC, atrazine in BPH, CDG and LBT;metolachlor in CLC, LBT, BCH, TRH2 and BPI;acetolachlor in BBH and BCH;azoxystrobin in BBH;desethylatrazine in BCH and BPI;metribuzin in BCH, TRH2 and BPI;and both clomazone and bromacil in sample BDC. A minimum reduction of 10.9% was found for metolachlor in sample BRH. Further reduction of pesticide residues up to 50% was recorded in the SMZ treatment as the concentrations of 4 out of 8 pesticide residues were reduced. This study confirms the potential of both the natural zeolite-Clinoptilolite, and SMZ of alleviating pesticide residues in water.

Technologic Tests of Turkey-Gordes Zeolite Minerals

Natural zeolites are found at many points of the world in the form of minerals. As for Turkey, quite large volumes of zeolites reserves are available in the following regions: Ankara (Nallihan, Beypazari, Polatli etc.), Kütahya-Sa- phane, Manisa-Gordes, Manisa-Demirci, Izmir-Urla, Balikesir-Bigadiçand Cappadocia. By means of the works carried out only at the field in Balikesir- Bigadiçregion, one of the detected reserves in Turkey, it was understood that an easily workable potential around 500 million ton is available. According to the very limited observations made until today, it is stated that the total reserve in our country may be around 500 billion ton. In these regions, the types of clinoptilolite, hoylandit, chabazite, analcime and erionite from the zeolite minerals exist. Zeolites are widely used in many sectors such as energy, environment, construction, detergent, chemistry, medicine, mining, agriculture and livestock. Zeolites also provide great benefits when they are used especially in agriculture and livestock for the purpose of preventing environmental pollution threatening human being. In this study, zeolite sample taken from Manisa-Gördes region was used. Following the processes of crushing and sieving, zeolite sample was subjected to chemical analyses according to their grain thickness, microscopic examination, the analyses of XRD and Technological Tests (ceramic pre-technological reviews, value of oil absorption, whiteness measurements, examination of the zeolite sample as cat litter, determination of bleaching capability, porosity values) and their ore characteristics were determined. After the analyses, ferrous oxide, biotite, quartz, muscovite, feldspar, chlorite, non-zeolite silicates and metamorphic rock fragments have been found. This zeolite mineral with high mineral purity has been suggested to clear off all impurities via ore preparation and enrichment methods.

The Use of Molecular-Sieving Materials as Ameliorant for Peat Degradation in the Tropics

Peat utilization for agriculture expansion area is commonly found extensively in tropical region during the last few decades. Most agronomical practices involve drainage resulting decomposition of organic materials and increasing drying. This study was carried out to determine the potential use of molecular-sieving materials (MPMs) as an ameliorant for peat soil targeted for reducing the potential hazard of peat degradation. A clinoptilolite-zeolite, empty fruit bunches of oil palm biochar (EFBOPB), and their combination were studied its characteristics to evaluate the ability in adsorbing water and green-house gas emission. A series of laboratory analyses were conducted to determine physicochemical and mineralogical characteristics of both materials and its combination, including elemental analyses, cation exchange capacity (CEC), pH, ore spaces, water holding capacity (WHC), and adsorption capacity for CO2, NH3, and N2. The study revealed that 100 - 150 mesh size of zeolite possesses higher values of CEC, WHC, and adsorption capacity for CO2, NH3, and N2 compared to EFBOPB, whereas the latter indicated a higher organic-C content and pore spaces. Combination of 75% (w/w) zeolite and 25% (w/w) EFBOPB showed the best composition of these two MPMs to improve WHC of peat and as consequences slowing down the firing process of the peat. Based on the gas adsorption data, it could be assumed that the mixture of MPMs studied could be considered as an effective material to reduce risk of peat from fire potential hazard and retard GHG emission.