Research Progress on Montmorillonite in the Production of Ruminants and its Main Function Mechanism

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Abstract:Montmorillonite(MMT) was a kind of laminated structure, composed of the aluminosilicate structure of SiAl and a small amount of FeCaMg and so onderived from a natural montmorilloniteand as a new feed additive in livestock production. The author mainly introduced the MMT of physical and chemical properties, the mechanism and application in ruminant production

Key words: Montmorillonite; Function; Mechanism; Ruminants

 近年来,随着饲料工业的迅速发展,黄曲霉毒素对饲料的污染问题已日渐严重,甚至破坏生态平衡,直接威胁到人类的健康,为此人们致力于开发新型脱霉剂来减缓这一现象;现在市场上销售的大部分脱霉剂的主要成分都是蒙脱石(montmorillonite)。蒙脱石已经作为一种新型添加剂而广泛用于动物日粮中来提高饲料品质,进而提高动物生产性能。从化学和矿物学的角度来看,蒙脱石经物理化学方法改性、加工纳米化后,具有更大比表面积,可大幅度提高吸附能力;蒙脱石分为天然蒙脱石和改性蒙脱石,改性蒙脱石比天然蒙脱石具有更强大的功能,成为畜牧生产中研究的热点;如纳米蒙脱石(MN)、载铜纳米蒙脱石(Cu-MMT)、载钠纳米蒙脱石(Na-MMT)、载钙纳米蒙脱石(Ca-MMT)等。

In recent years, with the rapidly development of the feed industry, the pollution of aflatoxins to feed has become more and more serious, even destroying the ecological balance, directly threatening human health. For this reason, people are committed to developing new mycotoxin binders to alleviate this phenomenon; The main ingredient of most mycotoxin binders currently on the market is montmorillonite (MMT). Montmorillonite has been widely used in animal diets as a new type of additive to improve feed quality, thereby improving animal production performance. From the perspective of chemistry and mineralogy, montmorillonite has a larger specific surface area after being modified by physical and chemical methods and processed into nanometers, which can greatly increase the adsorption capacity; montmorillonite is divided into natural montmorillonite and modified montmorillonite. Modified montmorillonite has more powerful functions than natural montmorillonite, and has become a research hotspot in livestock production, such as nano-montmorillonite (MN), copper-loaded nano-montmorillonite (Cu-MMT), and sodium-loaded Nano-montmorillonite (Na-MMT), calcium-loaded nano-montmorillonite (Ca-MMT), etc.

1  蒙脱石的理化特性

蒙脱石颗粒细小,0.2~1μm,硬度为2~2.5,相对密度2~2.7,甚柔软,有滑感。在电子显微镜下可见片状晶体,颜色呈白灰、浅蓝、红色等,颜色不一。加水膨胀,体积能增加几倍,并变成糊状物;具有很强的吸附力及阳离子交换性能。蒙脱石属酸性胶基,对强酸强碱具有一定的缓冲能力,因此能保持体系PH相对稳定。蒙脱石属于蒙皂石族二八面体亚族,由2层共顶联接的硅氧四面体片,夹1层共棱联接的铝(镁)氧(氢氧)八面体片构成 2∶ 1 型含结晶水结构,所谓“2∶ 1”是指蒙脱石每层结构由“两个”硅氧四面体片夹着“一个”铝氧八面体片构成。由于蒙脱石层间可因其它物质分子进出发生胀缩,因此可通过采用适当的物质对膨润土进行改性处理,从而达到对有害物质进行选择性吸附的目的;正是由于具有这种特殊的空间结构,蒙脱石才具有以下的特点。

1 Physical and chemical properties of montmorillonite

The montmorillonite particles are small, 0.2-1μm, hardness22.5, relative density 22.7, very soft and slippery. The flake crystals can be seen under the electron microscope, and the colors are white gray, light blue, red etc. with different colors. Adding water to swell, the volume can increase several times, and become a paste; it has strong adsorption and cation exchange performance. Montmorillonite is an acid gum base, which has a certain buffering capacity for strong acids and alkalis, so it can keep the PH of the system relatively stable. Montmorillonite belongs to the dioctahedral subfamily of the smectite group. It is composed of 2 layers of silicon-oxygen tetrahedral sheets connected by co-tops and a layer of aluminum (magnesium) oxygen (hydrogen oxygen) octahedral sheets connected by co-edges. 2: 1 The so-called "2:1" means that each layer of montmorillonite is composed of "two" silicon-oxygen tetrahedral sheets sandwiching "one" alumino-octahedral sheet. Since the interlayer of montmorillonite can expand and contract due to the entry and exit of molecules of other substances, the montmorillonite can be modified by using appropriate substances to achieve the purpose of selective adsorption of harmful substances; it is precisely because of this special The spatial structure, montmorillonite has the following characteristics.

 

1.1 吸附性 由于蒙脱石层间域的存在,不但具有外表面积,还具有内表面积,因此比表面积大,表面能也很高,使其具有较高的表面吸附能力。

1.1 Adsorption

Due to the existence of the interlayer domain of montmorillonite, it not only has an external surface area, but also an internal surface area. Therefore, the specific surface area is large and the surface energy is also high, which makes it have a high surface adsorption capacity.

1.2 离子交换性 由于蒙脱石存在类质同晶置换而产生负电荷,为了平衡电荷必须吸附环境中的阳离子,发生离子交换作用,主要阳离子如 Na+、Ca2+ 、K+、Mg2+ 、Li+、H+、Al3+ 等(杨献忠等,2003)。

1.2 Ion Exchange Ability.

Negative charge is generated due to isomorphous replacement of montmorillonite. In order to balance the charge, cations in the environment must be adsorbed and ion exchange occurs. The main cations are Na+, Ca2+, K+, Mg2+, Li+, H+, Al3+ (Yang Xianzhong et al., 2003).

1.3 电负性 蒙脱石硅氧四面体片中的硅离子和铝氧八面体片中的铝离子在晶体形成中常被低价的阳离子同晶替代使晶体带有大量负电荷,为平衡这些负电荷使晶体保持中性,经层间会吸附可交换性的阳离子,使得蒙脱石具有强大的静电吸附能力。

1.3 Electronegativity

The silicon ions in the silico oxide tetrahedral sheet and the aluminum ions in the aluminum oxide octahedral sheet of montmorillonite are often replaced by low-valent cation isomorphisms during the crystal formation, so that the crystal has a large number of negative charges, in order to balance these negative, the electric charge keeps the crystal neutral, and exchangeable cations will be adsorbed between the layers, making the montmorillonite possess strong electrostatic adsorption capacity.

1.4 吸水性 蒙脱石吸水性很强,吸水后膨胀,即晶格底面间距增大;蒙脱石在水介质中可分散呈胶体状态,受热自由水很快失去,100 ~ 200 ℃ 脱去吸附水,500 ℃时大量晶格水开始逸出。

1.4 Water-absorbent 

Montmorillonite is very water-absorbing, and expands after absorbing water, that is, the distance between the bottom surfaces of the crystal lattice increases; montmorillonite can be dispersed in a colloidal state in an aqueous medium, and the heated free water will quickly lose, and the adsorption will be removed at 100200 ℃ Water, a large amount of lattice water begins to escape at 500 ℃.

2   蒙脱石的作用机理

蒙脱石的作用机理主要取决于它的吸附性能和胶凝特性。蒙脱石吸附于消化道黏膜并吸附固定的病原微生物,使其破裂、脱水以至灭活;同时能在胃肠道中吸附其所产生的毒素,随粪便排出体外,消除病源,使机体处于有利环境中;蒙脱石与消化道黏液蛋白静电结合,可以增加黏液量并改善黏液质量提高黏液的内聚力和弹性,从而对消化道黏膜起保护和修复作用,抵抗外来制病因子的侵入(Girardeau,1987;Albengres 等,1985)。蒙脱石因有着较大的表面积、强大的吸附能力,能吸附受污染饲料中的霉菌和重金属,被广泛用作吸附剂、离子交换剂和抗菌剂。除此之外,蒙脱石还具有营养价值,因其含有丰富的矿物元素,可以用作饲料的改良剂和新型添加剂。饲料中添加蒙脱石可以改良饲料的品质,提高动物的生产性能、脱饲料中的霉菌毒素、吸附重金属、预防和治疗动物腹泻,抑菌和改善生产环境等一些功能。

2 The mechanism of action of montmorillonite

The action mechanism of montmorillonite mainly depends on its adsorption performance and gelling properties. Montmorillonite adsorbs on the mucosa of the digestive tract and adsorbs fixed pathogenic microorganisms, causing it to rupture, dehydrate and even inactivate; at the same time, it can absorb the toxins produced by it in the gastrointestinal tract, excreted with feces, eliminate the source of disease, and keep the body in a favorable environment Medium; the electrostatic combination of montmorillonite and digestive tract mucus protein can increase the amount of mucus and improve the quality of the mucus, improve the cohesion and elasticity of the mucus, thereby protecting and repairing the digestive tract mucosa, and resisting the invasion of foreign pathogenic factors (Girardeau, 1987 ; Albengres et al., 1985). Montmorillonite is widely used as adsorbent, ion exchanger and antibacterial agent because of its large surface area and strong adsorption capacity, which can adsorb mold and heavy metals in contaminated feed. In addition, montmorillonite also has nutritional value, because it is rich in mineral elements, it can be used as feed improver and new additive. Adding montmorillonite to feed can improve the quality of feed, improve animal production performance, remove mycotoxins in feed, adsorb heavy metals, prevent and treat animal diarrhea, inhibit bacteria and improve the production environment.

3 蒙脱石在反刍动物生产中的应用

3.1 脱霉菌毒素 在反刍动物上,已有研究结果表明,蒙脱石能提高动物生长性能、提高饲料利用率,减少肠道微生物的定植和减缓黄曲霉毒素的影响(Masoero等,2007;Stadler 等,1993)。黄曲霉和寄生曲霉产生的黄曲霉毒素B1 (AFB1 ),是目前已知最强的肝毒素,有致癌、致畸型和致突变作用。蒙脱石能有效地阻止动物肠壁对AFB1的吸收,因而可以减轻日粮中AFB1对人畜的毒性。不同条件下蒙脱石的吸收效率不同。齐德生等(2004)研究蒙脱石对黄曲霉毒素 B1(AFB1)的吸附作用中表明,蒙脱石在 pH 2.0和8.0条件下对AFB1的最大吸附量分别为613.5和628.9 μg/g;酸碱度在pH 2.0~8.0及温度在20~ 60 ℃时对吸附无明显影响。Ramos等(1996)描述了不同种类吸附剂对黄曲霉毒素的吸附效果,研究结果表明,蒙脱石能吸附约 1000μgAFB1 、425~450μg AFG 1 、230 μg AFG 2 和 200μgAFB2(AF 主要有B1、G1、G2和B2 ,B1为主要有毒物质)。蒙脱石相比吸附其他黄曲霉素而言,吸附AFB1效率最高。

3 Application of montmorillonite in ruminant production

3.1 Removel mycotoxins  In ruminants, existing research results have shown that montmorillonite can improve animal growth performance, increase feed utilization, reduce colonization of intestinal microorganisms and slow down the impact of aflatoxins (Masoero et al., 2007; Stadler et al. , 1993). Aflatoxin B1 (AFB1) produced by Aspergillus flavus and Aspergillus parasiticus is the strongest hepatoxin known at present and has carcinogenic, teratogenic and mutagenic effects. Montmorillonite can effectively prevent the absorption of AFB1 in the intestinal wall of animals, thus reducing the toxicity of AFB1 in diets to humans and animals. The absorption efficiency of montmorillonite is different under different conditions. Qi Desheng et al. (2004) studied the adsorption of montmorillonite on aflatoxin B1 (AFB1) and showed that the maximum adsorption capacity of montmorillonite on AFB1 under pH 2.0 and 8.0 conditions was 613.5 and 628.9 μg/ g; When the PH is between 2.0-8.0 and the temperature is between 20-60 ℃, the adsorption has no obvious effect. Ramos et al. (1996) described the adsorption effect of different kinds of adsorbents on aflatoxins, the research results showed that montmorillonite can adsorb about 1000μg AFB1, 425450μg AFG1, 230 μg AFG2 and 200μg AFB2 (AF mainly includes B1, G1 , G2 and B2, B1 is the main toxic substance). Compared with other aflatoxins, montmorillonite has the highest adsorption efficiency for AFB1.

3.2 吸附重金属  重金属在自然界中分布广泛,并且难以降解,因此重金属是一个严重环境污染问题。重金属是不能被动物所分解的,其在土壤中被植物利用,在动物摄取时,就会进入动物体内进行代谢,然后再排泄到土壤中,形成一个食物链,最终被人所消耗,造成重金属中毒。蒙脱石不仅可以控制残留农药的毒性,而且对饲料中重金属具有吸附作用,在饲料中适量添加可减轻重金属元素对动物的毒害作用进而解毒。Ivan等(2001) 证明在绵羊高铜日粮中按干物质重量的2%添加膨润土,能缓解在肝脏中铜的积累并可减轻绵羊铜中毒发病率及中毒症状,而对绵羊瘤胃发酵、十二指肠氨基酸及粗纤维代谢无不良影响。蒙脱石不仅能吸附饲料中的重金属,而且也能吸附水中的重金属。Bhattacharyya 等(2008)研究结果表明,蒙脱石有更高的吸附重金属能力,特别是其遇水能迅速膨胀,表面积立刻增大好几倍,因此适合处理水中重金属的污染。

3.2 Adsorb heavy metals  Heavy metals are widely distributed in nature and are difficult to degrade, so heavy metals are a serious environmental pollution problem. Heavy metals cann’t be decomposed by animals, they are used by plants in the soil. When they are ingested by animals, they will enter the animal’s body for metabolism, and then be excreted into the soil to form a food chain, which is eventually consumed by humans, causing heavy metal poisoning . Montmorillonite can not only control the toxicity of residual pesticides, but also has an adsorption effect on heavy metals in feed. Appropriate addition in feed can reduce the toxic effects of heavy metals on animals and detoxify. Ivan et al. (2001) proved that adding montmorillonite to sheep's high-copper diet based on 2% of the dry matter weight can relieve the accumulation of copper in the liver and reduce the incidence of copper poisoning in sheep and the symptoms of poisoning. Diodenal amino acid and crude fiber metabolism have no adverse effects. Montmorillonite not only can adsorb heavy metals in feed, but also can adsorb heavy metals in water. The results of Bhattacharyya et al. (2008) showed that montmorillonite has a higher ability to adsorb heavy metals, especially its rapid expansion when exposed to water, and its surface area immediately increases several times, so it is suitable for treating heavy metal pollution in water.

3.3 治疗腹泻  在畜禽生产中,幼龄动物往往会发生腹泻,尤其在刚出生10~20 d腹泻较为严重。蒙脱石能有效改善胃肠道黏膜,起到很好的修复作用。在断奶后7~10 d内,每天在饲槽前撒1次蒙脱石,可有效地降低应激反应。胡彩虹等(2006)研究结果表明,蒙脱石可有效阻断病原菌黏附,从而防治肠道细菌感染和细菌移位,维持肠道健康及其功能的正常发挥,进而可以预防和治疗腹泻的发生。

3.3 Treatment of diarrhea  In the production of livestock and poultry, diarrhea often occurs in young animals, especially diarrhea in the first 10-20 days of birth. Montmorillonite can effectively improve the mucosa of the gastrointestinal tract and play a good role in repairing. Within 7-10 days after weaning, sprinkle montmorillonite in front of the feeding trough once a day, which can effectively reduce the stress response. The research results of Hu Caihong et al. (2006) showed that montmorillonite can effectively block the adhesion of pathogenic bacteria, thereby preventing intestinal bacterial infection and bacterial translocation, maintaining intestinal health and normal function, thereby preventing and treating diarrhea. .

3.4 抑菌  蒙脱石对细菌有较强的杀菌作用。马玉龙等(2007)报道证明了Cu-MMT对细菌有较强的杀灭活性,与细菌发生吸附作用,使细菌细胞膜形态和通透性改变导致细胞内容物外泄而死亡。Cu-MMT对大肠杆菌的抗菌效能,是与静电吸附和铜离子的杀菌能力协同作用的综合结果。蒙脱石不仅能对大肠杆菌有杀菌功能,对金黄色葡萄球菌、霍乱弧菌、空肠弯曲菌、轮状病毒及胆盐都有较好的吸附作用(韩秀山等,2007)。蒙脱石还能阻断细菌黏附细胞的作用。蒙脱石吸附肠道内的有害菌群。由于具有特殊的表面结构,可以通过静电的相互作用把细菌吸附在其表面。胡秀荣等 (2002)、夏枚生等(2006)研究了天然蒙脱石对大肠杆菌和金黄色葡萄球菌相互作用,表明天然的蒙脱石并无抑菌或杀菌作用,只有吸附作用,但是可以用其他具有抑菌或杀菌作用的阳离子交换到蒙脱石层间,就会具有抑菌或杀菌的双重功能。

3.4 Bacteriostasis   Montmorillonite has a strong bactericidal effect on bacteria. Ma Yulong et al. (2007) reported that Cu-MMT has a strong killing activity on bacteria, and it adsorbs on bacteria, which changes the morphology and permeability of bacterial cell membranes and causes cell contents to leak and die. The antibacterial effect of Cu-MMT on Escherichia coli is a comprehensive result of the synergistic effect of electrostatic adsorption and copper ion sterilization. Montmorillonite not only has a bactericidal function against Escherichia coli, but also has a good adsorption effect on Staphylococcus aureus, Vibrio cholerae, Campylobacter jejuni, rotavirus and bile salts (Han Xiushan et al., 2007). Montmorillonite can also block the adhesion of bacteria to cells. Montmorillonite absorbs harmful bacteria in the intestine. Due to the special surface structure, bacteria can be adsorbed on the surface through electrostatic interaction. Hu Xiurong et al. (2002), Xia Meisheng et al. (2006) studied the interaction of natural montmorillonite on Escherichia coli and Staphylococcus aureus, indicating that natural montmorillonite has no antibacterial or bactericidal effect, only adsorption, but other The cations with antibacterial or bactericidal effect are exchanged between the montmorillonite layers to have the dual function of bacteriostasis or sterilization.

3.5 改善生产环境  蒙脱石因具有吸附效应和离子交换效应,所以在动物消化道内能选择性吸附NH3 H2S、CO2等气体,减少向大气中的排放。Opalinski 等(2009)研究结果表明,膨润土类吸附剂能有效地从畜体环境中吸附氨气。蒙脱石还能吸附体内的氨,减低瘤胃内液体氨的浓度,且可以对反刍动物日粮中补充尿素时出现的氨中毒起到预防的作用,同时提高氮的利用率。有研究结果表明,钠基膨润土能影响氮、钙、磷在绵羊体内的代谢,且低水平的添加量能提高高浓度粗饲料中尿素氮和磷的利用率(Martin等,1969)。

3.5 Improving the production environment  Montmorillonite has adsorption and ion exchange effects, so it can selectively adsorb NH3, H2S, CO2 and other gases in the animal digestive tract to reduce emissions to the atmosphere. The results of Opalinski et al. (2009) showed that montmorillonite adsorbents can effectively adsorb ammonia from the carcass environment. Montmorillonite can also absorb ammonia in the body, reduce the concentration of liquid ammonia in the rumen, and can prevent ammonia poisoning when urea is supplemented in ruminant diets, and at the same time improve nitrogen utilization. Studies have shown that sodium montmorillonite can affect the metabolism of nitrogen, calcium, and phosphorus in sheep, and low-level addition can increase the utilization of urea nitrogen and phosphorus in high-concentration roughage (Martin et al., 1969).

3.6 提高动物生产性能  蒙脱石能有效的吸附饲料中的黄曲霉毒素、重金属和抑菌等作用,进而促进畜禽生长,提高饲料利用率。蒙脱石能提高羊的日增重和羊毛生长,减少瘤胃内氨的浓度(Fenn等,1989,1990;Cobon 等,1992)。Huntington 等(1977)研究结果表明,添加4%和8%水平的膨润土能提高羊的日增重和饲料转化率,但是在后期处理组之间差异不显著。Walz等(1998)在羔羊日粮中添加0.75%膨润土能提高干物质采食量、平均日增重和血浆中尿素氮的浓度。林嘉等(2005)研究结果表明,日粮中添加 4%钠基膨润土的山羊其平均日增重显著提高(P<0.05),并提高了饲料转化率,获得了可观的经济效益,与 Walz 等(1998)报道一致。Dunn等(1979)研究结果表明,添加2%的钠基膨润土可以提高肉牛的生长性能。姬祥柱等(1992)用膨润土饲喂黄牛表明在日粮中添加50~100g膨润土,不仅可以提高育肥黄牛的增重效果,且可以提高饲料转化率,降低饲料成本,以添加100g膨润土为好。蒙脱石能提高奶牛产奶量,增加经济效益。孙茂红等(2000)在荷斯坦乳牛精料中每日添加240g纤维素酶、膨润土、尿素复合物制剂,能起到显著的增奶效果,而对乳脂率、乳密度无影响,且复合物制剂的效果比单一饲喂的效果要好。这可能是纤维素酶能加速分解瘤胃内的粗纤维,进而提高粗饲料消化率,而膨润土中的蒙脱石里含有大量的矿物质元素,是动物生长必不可少的,尿素作为一种氮源,补充瘤胃内蛋白,这种复合制剂可带来了很大的经济效益,将是以后的重点发展方向。

3.6 Improve animal production performance  Montmorillonite can effectively adsorb aflatoxins, heavy metals and antibacterial effects in feed, thereby promoting the growth of livestock and poultry and improving feed utilization. Montmorillonite can increase the daily gain and wool growth of sheep, and reduce the concentration of ammonia in the rumen (Fenn et al., 1989, 1990; Cobon et al., 1992). The results of Huntington et al. (1977) showed that the addition of 4% and 8% montmorillonite can increase the daily gain and feed conversion rate of sheep, but the difference between the post-treatment groups was not significant. Walz et al. (1998) added 0.75% montmorillonite to lamb diets to increase dry matter intake, average daily gain and plasma urea nitrogen concentration. The research results of Lin Jia et al. (2005) showed that the average daily gain of goats supplemented with 4% sodium montmorillonite in the diet increased significantly (P0.05), and the feed conversion rate was improved, and considerable economic benefits were obtained. (1998) reported consistent. Dunn et al. (1979) showed that the addition of 2% sodium montmorillonite can improve the growth performance of beef cattle. Ji Xiangzhu et al. (1992) feeding cattle with montmorillonite showed that adding 50-100g of montmorillonite to the diet can not only increase the weight gain of fattening cattle, but also increase the feed conversion rate and reduce feed costs. It is better to add 100g of montmorillonite. Montmorillonite can increase milk production of cows and increase economic benefits. Sun Maohong et al. (2000) added 240g of cellulase, montmorillonite, and urea compound preparation to Holstein dairy cow concentrate daily, which can increase milk significantly without affecting the milk fat rate and milk density, and the compound preparation The effect is better than that of single feeding. This may be that cellulase can accelerate the decomposition of crude fiber in the rumen, thereby improving the digestibility of roughage. The montmorillonite in montmorillonite contains a lot of mineral elements, which are essential for animal growth. Urea is used as a nitrogen source. , Supplement rumen protein, this kind of compound preparation can bring great economic benefits, it will be the key development direction in the future.

4 小结

蒙脱石所具有的层纹片状结构、非均匀性电荷分布、巨大的表面积和阳离子交换能力等特点,使其对饲料中的霉菌毒素有较好的吸附能力;同时能保护动物的胃肠道黏膜,对其进行保护、修复,防止因各种原因引起的腹泻。蒙脱石作为一种新型、环保型饲料添加剂,具有很好的应用效果,且价格低廉,具有深入开发的价值和广阔的应用前景。但是近年来,国内外蒙脱石应用于反刍动物的研究较少,特别是应用于泌乳奶牛对瘤胃细菌菌群和粪中菌群的影响,有待于更多的研究者做进一步研究。

4 Summary

Montmorillonite has the characteristics of lamellar and flake structure, non-uniform charge distribution, huge surface area and cation exchange capacity, so that it has good adsorption capacity for mycotoxins in feed; at the same time, it can protect the animal's gastrointestinal, the tract mucosa is protected and repaired to prevent diarrhea caused by various reasons. As a new and environmentally friendly feed additive, montmorillonite has good application effects, is low in price, and has the value of in-depth development and broad application prospects. However, in recent years, there have been few studies on the application of montmorillonite in ruminants at home and abroad, especially the effect of its application in lactating dairy cows on the rumen bacterial flora and fecal flora, which requires further research by more researchers.

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