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1.
固相萃取-高效液相色谱法测定有机肥中四环素类抗生素药物残留 总被引:6,自引:0,他引:6
建立了固相萃取-高效液相色谱(SPE-HPLC)法测定有机肥中土霉素(OTC)、四环素(TC)和金霉素(CTC)3种四环素类抗生素残留的方法。肥料样品采用甲醇、EDTA和McIlvaine缓冲液的混合液(pH=7.2)为提取液,用强阴离子交换柱(SAX)-亲水亲脂萃取柱(HLB)串联进行纯化和富集。采用甲醇-乙腈-0.01mol/L草酸溶液为流动相,进行HPLC分析。3种抗生素的线性范围为0.10~20 mg/L,OTC、TC和CTC的检测限分别为0.03、0.03和0.05 mg/L。不同添加水平的样品加标回收率为64%~86%,RSD在4.14%~8.16%之间。该方法测定了上海市场上40种肥料,发现部分样品有四环素类抗生素的残留物。 相似文献
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土壤磺胺类抗生素固相萃取-高效液相色 谱法的构建与优化 总被引:1,自引:0,他引:1
设计正交试验对红壤中磺胺甲恶唑(sulfamethoxazole, SMZ)的萃取方法进行优化,并结合高效液相色谱,构建了固相萃取-高效液相色谱联合测定法(SPE-HPLC),并将该方法应用于不同抗生素以及不同类型土壤中SMZ的提取测定。结果表明,在以乙腈–磷酸盐缓冲液为提取液、提取液量为10 ml、超声时间为15 min、9 ml甲醇淋洗固相萃取柱(HLB)的条件下,红壤中SMZ的提取效果最优,0.25 mg/kg的SMZ回收率达到85.58%,能够满足环境样品的分析要求。利用该法提取测定红壤中不同抗生素包括3种磺胺类抗生素(磺胺嘧啶、磺胺二甲基嘧啶、磺胺甲基嘧啶)和2种四环素类抗生素(土霉素、盐酸四环素),结果表明,当抗生素浓度为0.25 mg/kg时,磺胺类抗生素(SAs)的回收率范围在67.31%~85.58%,四环素类抗生素(TCs)的回收率范围在20.81%~59.33%。利用该法分别提取测定不同类型土壤中的SMZ回收率,得到潮土中SMZ的回收率最大,达到92.92%,其次为荒漠土、红壤、紫色土,最低的回收率出现在黄棕壤,仅为53.62%。据相关性分析表明,回收率与土壤电导率(EC)、微生物碳氮比(C/N)呈极显著负相关(P0.01),与阳离子交换量(CEC)、有机质(SOM)呈显著负相关(P0.05) 相似文献
3.
采用固相萃取(SPE)为样品前处理方法,建立了超高效液相色谱-串联四极杆质谱联用(UPLC-MS/MS)检测土壤中咪唑乙烟酸的残留分析方法。土壤样品经0.1 mol.L-1的氯化铵与氨水缓冲液(pH=10)超声提取、C18SPE柱净化后,应用超高效液相色谱串联四级杆质谱仪多离子反应监测(MRM)定量检测,分别以碎片离子m/z 290〉176和m/z 290〉245进行外标法定量。结果表明,在0.01~0.5mg.kg-1添加水平范围内咪唑乙烟酸的平均添加回收率在83.47%~101.70%之间;相对标准偏差在4.15%~5.28%之间;咪唑乙烟酸的定量检出限(LOQ)为0.075μg.kg-1。该方法灵敏度高,操作简单,定量准确,可用于土壤中咪唑乙烟酸的残留分析。 相似文献
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为建立蔬果中2,4-D残留量高效液相色谱(HPLC)检测方法,以固相萃取为净化手段,采用HPLC法检测番茄、葡萄、枇杷和黄瓜4种蔬果中2,4-二氯苯氧乙酸(2,4-D)的残留量。结果表明,样品经碱性水溶液提取、酸化,C18固相萃取小柱净化后,能够有效排除杂峰干扰,2,4-D残留量检测准确。该方法的线性相关系数为0.9980,检测限为0.0012 mg·kg~(-1),2,4-D的添加回收率为81.8%~116.0%,变异系数(CV)小于6%,表明方法准确度高,能满足番茄、葡萄、枇杷和黄瓜产品中2,4-D残留量的检测。采用此方法测定番茄等4种蔬果21份样品,样品中仅有2份番茄样品检测出2,4-D,残留量均小于0.02mg·kg~(-1)。本研究为利用HPLC检测果蔬中2,4-D残留量奠定了理论基础。 相似文献
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建立了固相萃取-高效液相色谱-质谱联用检测牛奶中地塞米松残留的方法.牛奶样品经乙酸乙酯提取,固相萃取柱净化,浓缩过滤后上机测定,标准加入法定量.结果显示,地塞米松在1~50ng/mL范围内,线性关系良好,相关系数r大于0.999,3个水平的平均加标回收率为65.7%~85.7%,相对标准偏差小于10%,方法定量限和检出... 相似文献
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建立了同时测定有机肥料中磺胺类、四环素类和喹诺酮类13种抗生素残留的高效液相色谱-串联质谱法,并对样品的前处理方法、仪器分析参数进行了优化。结果表明,13种抗生素在50~1 000 ng/mL间线性关系良好,相关系数均达到0.999以上,检出限在0.02~0.04 mg/kg,样品加标回收率在69%~111%之间,具有良好的重现性。该方法具有灵敏度高、准确度高等优点,可用于有机肥料中13种抗生素残留的同时检测。运用该方法在有机肥料实际检测中发现恩诺沙星、诺氟沙星、土霉素等抗生素残留。 相似文献
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采用室内模拟培养试验,研究了180 d内不同用量猪粪中3种四环素类抗生素(TCs)(包括四环素TTC,土霉素OTC,金霉素CTC)在土壤中降解的动态变化规律及降解途径。结果表明,猪粪中3种四环素类抗生素进入土壤后含量均呈现前期迅速下降,中后期减缓的规律,但不同种类和用量处理的变化速率和减少幅度有显著差异(P0.05)。180d时,猪粪处理土壤中的降解率为金霉素土霉素四环素,平均半衰期为17.43d、31.32d、49.48d。降解率与猪粪用量呈负相关,同培养时间呈正相关。猪粪中抗生素在土壤中的降解率要高于纯品抗生素,降解率的增加以外源微生物降解为主,外源微生物降解对四环素的作用最好。综上所述,随着培养时间的延长,猪粪中四环素类抗生素在土壤中能随微生物降解等作用而逐渐减少,但短期内仍可能产生环境危害。 相似文献
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为同时检测复杂基质中(由猪粪和蘑菇渣混合而成的堆肥原料)3种四环素类抗生素(四环素TC、土霉素OTC和金霉素CTC)及其代谢产物,建立了超高效液相色谱串联质谱检测方法(UPLC—MS/MS)。该方法同时采用pH值=4的Na2EDTA-Mellvaine缓冲溶液和乙腈为提取溶液,经过固相萃取净化后,以乙腈和0.1%的甲酸水溶液为流动相,采用超高效液相色谱柱进行分离,在电喷雾正离子模式下,用四极杆串联质谱仪进行定性和定量分析。3种四环素类抗生素及其代谢产物均在7min内完成分离,总共分析时间为12min。在0-6mg·kg^-1DW(Dryweight)浓度范围内,3种四环素类抗生素及其代谢产物的标准曲线线性良好,线性相关系数R2均大于0.9960,重现l生也较好(n=11,相对标准偏差均小于15%)。在3个加标水平0.2mg·kg^-1DW、1mg·kg^-1DW和4mg·kg^-1DW下,TC、OTC、CTC的回收率分别为71%-89%、66%~94%和66%~84%;去甲基金霉素(DMCTC)的回收率为52%-64%;差向异构产物的回收率在32%~51%之间;脱水产物以及差向脱水产物的回收率均低于30%。3种四环素类抗生素及其代谢产物的检出限和定量限分别在1.668~17.270μg·kg^-1和5.561—45.918μg·kg^-1范围内,表明该方法具有较高的灵敏度。对北京市某露天堆肥场中的样品进行测定发现,TC、OTC、CTC的浓度分别为0.4、1.6、2.9mg·kg^-1,检测到的代谢产物主要为相应的差向异构体,其中差向金霉素(ECTC)的浓度最高,达到2.7mg·kg^-1,和母体的含量水平比较接近,其他代谢产物也有不同程度的检出。 相似文献
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建立了基质固相分散萃取-高效液相色谱串联质谱法(MSPD-HPLC-MS/MS)测定土壤中3种磺酰脲类除草剂(氯磺隆、甲磺隆、苯磺隆)残留的分析方法。对基于球磨的基质固相分散萃取条件进行了详细优化,最终确定最佳条件为:0.2 g土壤样品、0.8 g HC-C18粉末状分散剂与直径为8 mm的小钢珠一起球磨10 min后,转移至空的玻璃萃取小柱,用10 m L乙腈洗脱,氮气吹干后用甲醇定容至0.6 m L,再经0.22μm的滤膜抽滤后装入自动进样瓶中。用Syncronis C18反相色谱柱分离,以甲醇(A)~1‰甲酸溶液(B)为流动相进行梯度洗脱,选择反应监测(SRM)模式下进行检测。氯磺隆在20~200μg·kg~(-1),甲磺隆和苯磺隆在10~200μg·kg~(-1)范围内线性良好,相关系数r在0.997 9~0.999 5。土壤样品的平均加标回收率在84.7%~104.6%,相对标准偏差在4.5%~7.9%(n=5)。方法的检出限(S/N=3)0.32~0.68μg·kg~(-1)。该方法简单、效率高、干扰少、回收率高,满足土壤中除草剂的残留分析要求。 相似文献
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壤和堆肥中四环素类抗生素的检测方法优化及其在土壤中的降解研究 总被引:2,自引:0,他引:2
在对土霉素(OTC)、四环素(TC)和金霉素(CTC)3 种四环素类抗生素的高效液相色谱(HPLC)检测分析方法以及在土壤和堆肥中的提取方法进行改进和优化的基础上,采用该方法进行了 3 种抗生素在土壤中的降解试验。结果表明,选用 Agilent Eclipse XDB-C8(4.6150 mm,5 m)色谱柱,以 0.01 mol/L草酸/乙腈/甲醇(79/10.5/10.5,v/v/v)为流动相,紫外检测波长 268 nm,流速 1.0 mL/min,进样量 5 L,采用外标法定量,可使 3 种四环素类抗生素在 20 min 内全部洗脱并达到基线分离; 在 0~10 mg/L 范围内,抗生素浓度与峰面积呈显著的线性关系,相关系数(r)均 0.999。土壤和堆肥样品中的 OTC、TC 和 CTC可用1 mol/L NaCl/0.5 mol/L 草酸/乙醇(25/25/50,v/v/v)混合溶液提取,其回收率在 76.0%~92.5% 之间。加入到土壤中的抗生素在 25℃下避光培养 49 d 后,在壤土和红土中的降解率分别是 67%~72% 和 36%~46%,对应的半衰期分别为 2630 d 和 4675 d,说明抗生素在壤土中比红土中容易降解。此外,3种抗生素在壤土中的半衰期没有显著性差异,而在红土中 CTC 和 TC 的降解速率显著高于 OTC。 相似文献
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绿肥对植烟土壤酶活性及土壤肥力的影响 总被引:18,自引:2,他引:18
通过田间试验,研究翻压绿肥对植烟土壤酶活性及土壤肥力的影响。结果表明, 翻压绿肥能够明显提高土壤酶活性和土壤肥力水平,当绿肥翻压量在15000 kg/hm2以上时,尤其在22500~30000 kg/hm2之间时对土壤各项指标的影响更加明显。与对照相比,翻压绿肥的各处理土壤脲酶、 酸性磷酸酶、 蔗糖酶、 过氧化氢酶增幅分别为13.10%2~3.81%、 12.92%~29.38%、 75.35%~234.51%、 29.17%~37.08%; 土壤有机质、 全氮、 碱解氮、 有效磷、 速效钾、 pH、 孔隙度增幅分别为13.01%~70.41%、 6.42%~27.52%、 1.14%~10.99%、 15.97%~34.99%、 10.28%~38.30%、 2.74%~7.05%、 0.19%~2.50%,土壤容重降幅为1.47%~5.15%。简单相关分析表明,脲酶、 酸性磷酸酶、 蔗糖酶、 过氧化氢酶4种酶之间以及4种酶与土壤理化因子之间均有极显著的相关关系,而土壤酶活性之间的相互关系表明,土壤酶在促进土壤有机物质转化中不仅显示其专性特性,同时也存在共性关系; 典型相关分析结果为,第一对典型变量线性函数反映了土壤酶活性和土壤养分因子对土壤综合肥力水平的影响,第二对典型变量线性函数反映了施入绿肥对土壤内部重要的生理生化过程变化的影响; 主成分分析结果显示,第一主成分反映了土壤的综合肥力水平,所有因子均对土壤肥力水平起到了正效应,土壤酶活性能够和土壤理化因子共同评价土壤综合肥力水平。以上结果说明,翻压绿肥后土壤生物过程活跃,有利于土壤有机物质的转化和烤烟正常生长所需的营养供应。 相似文献
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Crop response to manure application may extend beyond the year of application due to residual nutrient availability. A field experiment was conducted to evaluate feedlot manure application (at 0 22.5, 45, 90 and 180 Mg ha?1) and subsequent residual effects (24-yr) on wheat and sorghum grain yields. Sorghum grain yields increased significantly with manure and nitrogen (N) fertilizer application. However, winter wheat grain yield showed no consistent response to manure and fertilizer application in the 9-yr when manure was applied. Averaged across the subsequent 24 years, residual feedlot manure and annual N fertilizer application significantly increased sorghum and winter wheat grain production. Application of cattle manure did increase soil organic matter content, pH and plant available soil nutrients. Our finding showed that growers could take advantage of the long-term benefits of nutrients supplied from manure application to bolster crop production, improve soil quality and reduce fertilizer input cost. 相似文献
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A. O. Shokalu M. T. Adetunji J. G. Bodunde H. A. Akintoye J. O. Azeez 《Archives of Agronomy and Soil Science》2017,63(8):1070-1081
Soil contamination with heavy metals is of great concern worldwide because of its negative effects on human health and environment. The objective of this study was to evaluate the influence of poultry manure on cadmium (Cd) adsorption characteristics in soils from ten different land uses and to determine the effects of Cd adsorption on soil properties. Laboratory experiments were carried out using Cd concentrations ranging from 0 to 160 mg Cd L?1 and poultry manure rates ranging from 0 to 8% w/w basis. Results showed that all the soils exhibited varying capacity to adsorb Cd with values ranging from 28.78 to 130.2 mgkg?1; 126.2 to 153.5 mgkg?1 and 126.2 to 156.1 mgkg?1 for 0%, 4% and 8% poultry manure at 160 mgkg?1 initial Cd concentrations, respectively. Lowest Cd adsorbed (28.78 mgkg?1) was recorded in samples from 6 months fallow and highest (156.1 mgkg?1) from vegetable field. On the average, capacity to adsorb Cd was 72.1%, 99.7% and 95.3% with 0%, 4% and 8% applied poultry manure, respectively. Organic carbon, CEC, pH were significantly correlated with Cd adsorption. Poultry manure use will increase Cd adsorption and decrease Cd in the environment. 相似文献
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针对施用粪肥导致的我国集约化种养区域农田土壤磷素高量累积和高环境风险问题,利用长期定位试验定量分析了施用粪肥对农田土壤磷素累积和磷饱和度(DPS, degree of P saturation)增加速率(每年1 kg P·hm-2磷素盈余所导致的土壤磷素含量或DPS变化量)的影响。结果表明:连续22年过量磷素投入明显提高了土壤磷素含量和DPS,0~20 cm土层土壤磷素累积、DPS增加与磷素盈余均存在明显的线性相关性。与单施化肥相比,施用粪肥对土壤全磷的累积速率影响不大,但是明显提高了土壤Olsen-P累积和DPS增加速率。施用粪肥下,每年1 kg P·hm-2的磷盈余所导致的0~20 cm土层土壤Olsen-P、CaCl2-P累积和DPS增加量分别为0.071 mg P·kg-1(r=0.608, P=0.029)、0.003 mg P·kg-1(r=0.528, P=0.066)和0.036%(r=0.863,P=0.002),分别为不施粪肥的3.3、6.0倍和1.2倍。土壤DPS变化与磷含量变化之间也存在明显的线性关系,0~20 cm土层土壤每年全磷、Olsen-P和CaCl2-P含量增加1 mg P·kg-1所导致的土壤DPS增加值分别为0.13%、0.42%和7.78%。20~40 cm土层土壤磷素累积、DPS增加与磷素盈余之间的线性相关性均较差,但与0~20 cm土层相比,施用粪肥和不施粪肥之间累积速率的差异性有增大的趋势,说明施用粪肥促进了磷素向下层土壤的移动。施用粪肥加速了土壤有效磷累积和DPS增加,进而提高了土壤中磷素损失风险,合理施用粪肥是控制集约化种养区域农田磷面源污染的关键。 相似文献
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D.A.L. Leelamanie Jutaro Karube U.I. Samarawickrama 《Soil Science and Plant Nutrition》2013,59(5):683-691
Aggregate slaking is linked with rapid pressure buildup within aggregates. Soil water repellency may help hamper the pressure buildup within aggregates by reducing their wetting rates. We examined the effects of animal manure in improving aggregate stability, the hydrophobic effects of green manure, and the possibility of using organic manure mixtures to increase the aggregate stability for Sri Lankan red yellow podzolic soils using model aggregates. Almost all the cow dung (CD) added samples showed extremely low percentages of water stable aggregates (%WSA) demonstrating rapid destruction of aggregates. Although the addition of ≥ 10% goat dung (GD) improved the %WSA, aggregate floating occurred, showing the risk of aggregate floating with runoff water. Addition of 5% GD would be an acceptable solution if the %WSA can be improved. Casuarina equisetifolia L. leaves (CE) was found to be a hydrophobic green manure. Although addition of ≥ 5% CE increased the %WSA up to about 90%, aggregate floating occurred. The possibility of improving %WSA using 1–2% hydrophobic green manure in organic manures mixtures was tested. Samples with 5% GD + 2% CE manure mixture showed the highest and the most stable %WSA without showing aggregate floating. Additions of compost and poultry litter were found not to be effective in improving aggregate stability with or without CE. Strong or higher water repellency was not observed in any of the samples with manure mixtures, showing that the addition of 1–2% hydrophobic CE would not induce detrimental effects of water repellency. There was no clear correlation between %WSA and the hydrophobicity of soils. However, the %WSA can be considered to show a tendency to increase with increasing hydrophobicity, because the %WSA was very high in samples with hydrophobic CE, the %WSA increased when mixed with 1–2% CE, and samples with highest water drop penetration time (WDPT) among all the manure mixtures showed the highest %WSA. 相似文献
17.
AbstractThe effect of organic manure and inorganic fertilizer on soil aggregate size distribution and stability, and associated carbon (C) within aggregates varies greatly in previous studies because of the differences in soil conditions, cropping systems, and management practices. This study was conducted as two field fertilization experiments, with different cropping systems, under a subtropical climate in China. The two field experiment sites were located in Jinhua (established in April 2011) in the Jinqu basin in Zhejiang province and Jintan (established in October 2010) in the low-middle Yangtze River plain in Jiangsu province. Both experiments consisted of four treatments, including unfertilized (CK), mineral fertilizer nitrogen (N)–phosphorus (P)–potassium (K) (NPK), NPK plus straw (NPK?+?SR), and NPK plus cattle manure (NPK?+?FYM) or half NPK plus cattle manure (1/2NPK?+?FYM). Water stable aggregate size classes (>5, 2–5, 1–2, 0.5–1, 0.25–0.5, and <0.25?mm) and associated soil organic C (SOC) at 0–15?cm depth were measured. The mean weight diameter (MWD), geometric mean diameter (GMD), and water stable aggregates (WSA)?>?0.25?mm were also determined. The results showed that aggregate-size distribution varied with soil types. Combined application of NPK and organic matter (straw residue or cattle manure), unlike the CK and NPK treatments, significantly increased the WSA >0.25?mm, MWD, and GMD, while obviously reducing the proportion of <0.25?mm aggregates. However, no differences in WSA >0.25?mm, MWD, GMD, and associated C were observed between CK and NPK at both sites. The addition of FYM to the NPK treatment yielded the highest SOC contents in bulk soil, and showed significantly higher associations of C within all size aggregates at both sites. In contrast, NPK?+?SR significantly increased SOC within aggregate classes (2–5?mm, 0.5–1?mm, 0.25–0.5?mm, and <0.25?mm) at Jinhua and (>5?mm and 1–2?mm) at Jintan compared to the CK and NPK treatments. Overall, the combined application of FYM and mineral NPK was the best sustainable management practice for the improvement of aggregate stability and SOC sequestration. 相似文献
18.
连续施用不同比例鸡粪氮对水稻土有机质积累及土壤酸化的影响 总被引:9,自引:1,他引:9
【目的】土壤酸化是自然过程。随着农业集约化发展,土壤酸化在部分农田呈加速趋势,而施肥是目前农田土壤酸化加速的重要诱因,研究有机肥和化肥对土壤酸化的作用差异及机理,对合理指导施肥及耕地保育有重要的意义。【方法】通过测定不同施肥处理的不同组分有机质含量及酸碱缓冲容量,探明不同施肥处理的酸化影响,从土壤有机质和盐基累积角度对有机-无机肥料不同比例配施条件下土壤酸化特征进行了研究。【结果】① 连续5年在等氮量(N 270 kg/hm2)且有机-无机肥料不同配施比例的处理中,水稻产量以有机肥比例为25%~50%的处理最高,其平均产量比单施化肥处理提高了5.1%,比对照提高44.9%。但处理间无显著性差异;② 土壤各活性有机质及总有机质等指标中仅总有机质含量随鸡粪施用比例的增加而持续增加,不同比例有机无机肥配合施用后,土壤的高活性有机质及低活性有机质均高于CK和纯化肥氮处理,但随着有机肥投入比例的升高,除中活性有机质和水稻产量之间呈显著的正相关外(P=0.0067**),高活性有机质、活性有机质及总有机质含量与水稻产量之间的相关性不显著(对应的概率值分别为P=0.192,P=0.208,P=0.160);③ 施肥提高了土壤的碳库管理指数(CPMI),且其随有机肥施用比例的上升呈增加趋势。增施鸡粪提高土壤的交换性盐基离子(Ca2+、 Mg2+、 K+、 Na+)含量,导致阳离子代换量(CEC)和pH随鸡粪施用比例的提高而升高。供试土壤酸碱缓冲容量为2.07~2.36 cmol/kg,随鸡粪施用比例的上升而增加,其与土壤阳离子代换量及有机质含量呈显著正相关。表明增施鸡粪可使土壤pH及酸碱缓冲容量上升,与鸡粪使土壤盐基累积量及有机质含量的提高有关。【结论】连续有机-无机肥施用下,土壤pH上升和酸碱缓冲容量的提高可能与该试验点下盐基离子和有机质含量随鸡粪施用比例上升有关,但其最终上升幅度及平衡点尚需进一步研究。鸡粪氮替代化肥氮比例为25%~50%时,土壤性质最优,水稻产量最高。 相似文献
19.
四环素类抗生素在土壤和堆肥中的吸附和降解 总被引:6,自引:0,他引:6
Two agricultural soils were collected from Dahu and Pinchen counties and swine manure compost (SMC) from Ping-tung County in Taiwan, China to investigate the sorption and dissipation of three tetracyclines (TCs), i.e., oxytetracycline (OTC), tetracycline (TC) and chlortetracycline (CTC), in compost, soils and soil/compost mixtures with different organic carbon (OC) contents. There were seven treatments in total. TCs were most strongly adsorbed to SMC in all treatments due to the high OC content. When SMC was present in the soils, the sorption of TCs was significantly enhanced, which might be attributed to the increased OC content and CEC. The adsorption of TCs showed non-linear adsorption isotherms and fitted well to the Freundlich model. After 49 d of incubation at 25 ℃ in soils and soil/compost mixtures in the dark, TCs elapsed in all substrates, with the time required for 50% degradation (DT50) between 20 and 41 d, and the time for 90% degradation (DT90) between 68 and 137 d. Soil amended with compost enhanced the stability of TCs and reduced their mobility. The dissipation of TCs in a soil environment was slow, indicating that these compounds might be persistent in soil. 相似文献