抗生素在土壤中的归趋及不可提取态残留

抗生素是近年来备受关注的一种新兴环境污染物,进入环境后会被降解或残留在环境介质和环境生物体内.在土壤中形成不可提取态残留(NERs)是抗生素重要的环境归趋,然而有关土壤中抗生素NERs形成机理和环境风险的研究尚处于起步阶段.NERs的形成能在一定程度上降低抗生素的环境危害,但当土壤环境条件改变时NERs仍有重新释放的潜...     

化学农药污染土壤植物修复中的环境化学问题

报道了利用植草修复受DDT，BHC和Dicofol污染的研究，讨论了化学农药污染土壤植物修复中,农药在植物中富集与在土壤中降解以及结合残留等环境化学问题。研究表明，在植物修复的过程中，通过草对农药吸收的途径而去除土壤中污染物的作用所作的贡献很小，植草的作用可能是通过草的根部向土壤释放酶和某些分泌物，从而激发土壤中微生物的活性，并加速农药生物降解作用的结果。草在不同土壤中修复能力的差异，可能与不同土壤中所存土著微生物的差异以及其活性受酶和某些分泌物所激发差异的结果。选择能使根际区产生强烈的生物降解作用的草品种，是利用草作为化学农药污染土壤修复的关键。土壤与植株中农药结合残留的形成可能是土壤中污染物消除的又一个重要因素。     

生物炭的老化及其对温室气体排放影响的研究进展

生物炭是生物质在无氧或限氧条件下经高温热解后产生的多孔富碳物质,其被广泛施加到土壤中改良土壤性质,调节温室气体排放。生物炭施入土壤后,长期受外界物理、化学和生物等环境作用导致生物炭性质发生缓慢改变,这个过程称为生物炭的老化。文章综述了原位生物炭自然老化和实验室模拟老化的方法以及老化后生物炭理化性质的变化,从理化性质变化的角度论述了生物炭老化过程对二氧化碳(CO_2)、甲烷(CH_4)和氧化亚氮(N_2O)这3种温室气体排放的影响,并初步解释生物炭老化过程对增加或减少温室气体排放的可能机制。主要内容如下:生物炭老化方法可以分为自然老化和人工模拟老化,模拟老化方法包括生物、物理和化学老化。生物炭发生老化后,生物炭的比表面积(SSA)和孔容根据老化强度而有不同变化,自然或人工模拟的温和老化方法使生物炭表面上有新的纳米微孔生成,生物炭SSA增加,而使用强酸或强氧化剂的强烈老化方式可破坏生物炭孔隙结构,导致SSA和孔容下降。从化学性质方面来讲,生物炭C/N比随老化过程而降低,但是O/C比却随老化过程而升高;此外,当生物炭老化时,生物炭表面含氧官能团增加,例如羧基、羰基和酚基等,这些含氧基团可以和阳离子结合形成羧酸盐和酚盐,同时释放H~+,导致老化生物炭的pH值降低。基于有限的研究报道,老化生物炭仍然具有一定的CH4减排潜力,这得益于土壤通气状态的改善和甲烷氧化菌氧化CH_4潜力提升。相反,由于生物炭极性增强和pH值降低,生物炭老化过程有促进土壤有机质矿化增加CO_2和N_2O排放的趋势。然而为了辅正这一论断,准确评估生物炭老化的环境效应,长期原位生物炭老化并同时设置新鲜生物炭对照的研究需要进一步开展,以探明生物炭老化过程对温室气体排放的影响机制,为生物炭生产和合理施用提供科学应用指导。     

溴氰菊酯的结合残留

本工作研究了溴氰菊酯在土壤及黄豆植株中结合残留物的生成。结果表明:土壤中结合残留的形成过程与土壤中微生物的作用密切相关。生成的结合残留物主要存在于土壤腐黑质中。黄豆植株中结合残留物生成实验表明:结合残留物主要结合在植物体的木质素和纤维素组分中。结合残留物既有母体化合物,也有水解和氧化代谢物。这一结果支持了结合残留形成过程牵涉到物理和化学两种作用的观点。     

超临界流体萃取在研究土壤和沉积物结合态残留中的应用

许多有机污染物在土壤和沉积物中形成持久稳定的结合态残留；结合态残留对土壤和沉积物的解毒过程、污染物长期分配行为、生物可用性和生物毒性都具有重要影响。为了揭示结合态残留的形成机制及其对污染物环境行为和毒理学参数的影响，从土壤或沉积物中提取出不同结合状态的有机污染物就显得非常重要。超临界流体萃取(SFE)可以实现选择性萃取，从而得到有关污染物一基体间相互作用的信息。文章介绍了SFE应用类型、超临界流体种类以及影响SFE萃取率的因素，对SFE模拟有机污染物长期吸附／解吸行为和生物可用性研究进行了论述，并认为SFE势必发展成为土壤或沉积物中结合态残留形成机理研究、土壤修复和生态风险评价的一种强有力的技术。     

不同重金属对土壤中四溴双酚A环境归趋的影响

四溴双酚A(TBBPA)和重金属的复合污染情况常见于电子电器拆解厂或回收站周边土壤,而重金属对TBBPA在土壤环境中的降解、转化和残留的影响尚不清晰.本研究利用14C标记的TBBPA来探索不同浓度水平重金属(Cu、Cd和Zn)对两种土壤(红壤和乌栅土)中TBBPA降解转化、矿化、不可提取态残留形成等环境行为的影响.经60 d培养,乌栅土中92.2%±0.5%的TBBPA被转化为不可提取态残留或代谢产物,其中7.2%±0.8%被彻底矿化为CO2;灭菌作用极大地抑制了乌栅土中TBBPA不可提取态残留的形成(由77.2%降至9.9%),表明土壤微生物在不可提取态残留的形成中起到关键作用.而红壤中仅有9.9%±0.5%的TBBPA被转化成不可提取态残留,<0.5%被矿化为CO₂,与灭菌对照组无显著差异.当土壤重金属(>500μmol·kg-1)存在时,乌栅土中TBBPA矿化和不可提取态残留形成率分别降低14%—78%和31%—86%,而可提取态TBBPA(即生物可利用态)增加0.5—4.4倍,其中水溶态残留增加0.3—1.5倍,进而增加TBBPA在土壤中的持久...     

农药与土壤腐殖物质的结合残留及其环境意义

农药或其代谢产物进入土壤环境后，可通过多种途径与土壤无机和有机组分形成结合残留物。越来越多的证据表明，在农药土壤环境行为的研究中，应重视其结合残留问题。文章阐述了农药在土壤中的主要结合残留机理，结合残留物在土壤腐殖物质各组分中的分布状况及其环境意义，并对该领域的深入研究提出建议。     

EGTA淋洗和KH2PO4钝化联合修复重金属污染土壤

为进一步削减螯合淋洗后土壤残留重金属的环境风险,采用淋洗与钝化相结合的方法修复重金属污染土壤.研究了乙二醇双(2-氨基乙基醚)四乙酸(EGTA)淋洗、磷酸二氢钾(KH_2PO_4)钝化及两者联合修复对土壤重金属洗脱率的影响,并分别采用TCLP法和BCR法分析重金属浸出浓度及化学形态分布,构建了涵盖土壤重金属残留量、生物有效性和毒性的环境风险评价方法,对淋洗、钝化及其联合修复效果进行了评价.结果表明,EGTA对Cu和Cd具有较好的洗脱效果,降低了土壤Cu、Zn和Cd浸出浓度,提高了Pb浸出浓度,削减了可还原态Cu残留量、弱酸提取态和可还原态Zn残留量、可还原态Pb残留量以及弱酸提取态、可还原态Cd残留量.随着KH_2PO_4投加量的增加,Pb、Cd和Cu浸出浓度呈下降趋势,Zn浸出浓度先上升后下降.KH_2PO_4对重金属形态分布的影响主要表现为降低弱酸态或可还原态重金属占比,提高残渣态重金属占比.EGTA和KH_2PO_4联合修复显著降低了4种重金属的可还原态残留量和弱酸提取态Pb、Cd残留量,大幅度削减了Cd和Cu的浸出浓度和环境风险.Zn污染土壤宜淋洗修复,Pb污染土壤宜钝化修复,Cd和Cu污染土壤深度修复宜淋洗/钝化联合处理.     

土壤中持久性有机污染物不可提取态残留的测试方法、生成特征与环境风险研究进展

持久性有机污染物（persistent organic pollutants,POPs）是一类具持久性、高生物蓄积性、高毒性且具长距离迁移性的高关注度化学物质,土壤是其主要储存库. POPs进入土壤后,与土壤结合发生老化现象,一部分生成不可提取态残留（non-extractable residue,NER）.作为POPs环境归趋中的重要过程,NER的生成传统上被视为污染物的去毒或降解途径;但随着老化时间的增加或者受环境条件变化等因素的影响,土壤中NER可能会再次释放,造成环境风险.国内外有关土壤有机污染物NER的研究已有较多报道,但其中关于POPs-NER的报道相对欠缺.本文介绍了POPs-NER的同位素测试手段和生成机理,对特定组分NER的测试方法、POPs-NER生成的动力学模型与影响因素以及POPs-NER的释放与环境风险等方面的研究进展进行了综述,并简要分析了当前POPs-NER研究领域的局限和未来需要关注的问题.由于部分研究方向缺乏POPs-NER的案例,本文分析了一些非持久性有机污染物NER的相关研究,以期为今后POPs-NER的研究提供参考.     

改性生物炭对菜地土壤磷素形态转化的影响

生物炭是一种含碳量高且更为稳定的有机碳,能够显著影响土壤物理、化学及生物学性质。以华南地区主要的菜地土壤为研究对象,研究新型生物炭对土壤磷素形态转化及有效性的影响,结果表明,施用生物炭可以提高树脂磷(Resin-Pi)、NaHCO3提取态无机磷(NaHCO3-Pi)、NaOH提取态无机磷(NaOH-Pi)含量,生物炭施入土壤后能明显提高土壤的有效磷含量,但并未显著提高稀盐酸提取态无机磷(D·HCl-Pi)和浓盐酸提取态无机磷(C·HCl-Pi)的含量;施用生物炭增加了NaHCO3提取态有机磷(NaHCO3-Po)的含量,降低了NaOH提取态有机磷(NaOH-Po)的含量,提高了残渣磷(Residual-Pt)含量,并未改变浓盐酸提取态有机磷(C·HCl-Po)的含量。土壤速效磷与Resin-Pi、NaHCO3-Pi、NaHCO3-Po、NaOH-Pi、D.HCl-Pi、Residual-Pt呈显著相关,并与NaHCO3-Pi的相关性最强,相关系数达到0.980 5;Resin-Pi与NaHCO3-Pi、D.HCl-Pi呈极显著相关;NaHCO3-Pi与NaOH-Pi、D.HCl-Pi、Residual-Pt呈显著相关,并与D.HCl-Pi的相关性最强,相关系数达到0.816 6。表明在施用生物炭的条件下,不同形态的磷可以通过矿化等形式转化为有效性较高的磷形态。     

The metabolism and distribution of [14C‐phenyl]‐ethyl parathion in a tropical soil under field conditions

The persistence, distribution and metabolism of [^l4C‐phenyl]‐ethyl parathion applied to soil columns in an agricultural farm were investigated under tropical field conditions. Volatilization, soil microbial activity, moisture levels and pH were found to influence the persistence, distribution and metabolism of this pesticide in the soil. There was rapid distribution of the pesticide in the soil matrix with time resulting in high levels of bound residues which reduced the overall rate of disappearance of parathion residues from the soil. The soil was slightly acidic but the metabolites, paraoxon, p‐nitrophenol and p‐aminophenol were detected in the soil extracts 7 days after pesticide application. After 72 days, 43.7% of the applied pesticide remained in soil composed of 18.9% extractable and 24.8% bound residues. A mechanism for the metabolism of ethyl parathion in this soil is given.     

A unified approach for including non-extractable residues (NER) of chemicals and pesticides in the assessment of persistence

All chemicals form non-extractable residues (NER) to various extents in environmental media like soil, sediment, plants and animals. NER can be quantified in environmental fate studies using isotope-labeled (such as ¹⁴C or ¹³C) tracer compounds. Previous NER definitions have led to a mismatch of legislation and state of knowledge in research: the residues are assumed to be either irreversibly bound degradation products or at least parts of these residues can be released. In the latter assumption, soils and sediments are a long-term source of slowly released residues. We here present a conceptual experimental and modeling approach to characterize non-extractable residues and provide guidance how they should be considered in the persistence assessment of chemicals and pesticides. Three types of NER can be experimentally discriminated: sequestered and entrapped residues (type I), containing either the parent substance or xenobiotic transformation products or both and having the potential to be released, which has indeed been observed. Type II NER are residues that are covalently bound to organic matter in soils or sediments or to biological tissue in organisms and that are considered being strongly bound with very low remobilization rates like that of humic matter degradation rates. Type III NER comprises biogenic NER (bioNER) after degradation of the xenobiotic chemical and anabolic formation of natural biomolecules like amino acids and phospholipids, and other biomass compounds. We developed the microbial turnover to biomass (MTB) model to predict the formation of bioNER based on the structural properties of chemicals. Further, we proposed an extraction sequence to obtain a matrix containing only NER. Finally, we summarized experimental methods to distinguish the three NER types. Type I NER and type II NER should be considered as potentially remobilizable residues in persistence assessment but the probability of type II release is much lower than that of type I NER, i.e., type II NER in soil are “operationally spoken” irreversibly bound and can be released only in minute amounts and at very slow rates, if at all. The potential of remobilization can be evaluated by chemical, physical and biological methods. BioNER are of no environmental concern and, therefore, can be assessed as such in persistence assessment. The general concept presented is to consider the total amount of NER minus potential bioNER as the amount of xenoNER, type I?+?II. If a clear differentiation of type I and type II is possible, for the calculation of half-life type I NER are considered as not degraded parent substance or transformation product(s). On the contrary, type II NER may generally be considered as (at least temporarily) removed. Providing proof for type II NER is the most critical issue in NER assessment and requires additional research. If no characterization and additional information on NER are available, it is recommended to assess the total amount as potentially remobilizable. We propose our unified approach of NER characterization and evaluation to be implemented into the persistence and environmental hazard assessment strategies for REACH chemicals and biocides, human and veterinary pharmaceuticals, and pesticides, irrespective of the different regulatory frameworks.     

畜禽养殖排放的雌激素对周边水体环境的影响

环境雌激素是一大类化学物质,它们能够干扰生物体内激素的合成、分泌、转运、活性等,或与生物体内激素结构相似而发挥激素作用,对生物体的生长、繁殖及行为产生不利影响。环境雌激素包括天然雌激素及人工合成类雌激素。随着国内畜禽养殖的规模与数量的不断扩大,养殖场成为了一个很大的环境雌激素的产生源,其环境风险应得到相应的重视。目前对畜禽养殖过程中环境雌激素的产生量以及雌激素进入环境后的迁移转化行为已有很多的研究,包括野外的调查与实验室内机理研究。畜禽养殖过程产生的大量雌激素进入环境后能够被土壤吸附及微生物降解。室内的静态平衡吸附实验、土柱迁移试验及降解研究均表明雌激素进入环境后绝大部分迅速被吸附到土壤颗粒或悬浮胶体、沉积物颗粒上,同时发生转化与生物降解,由此推断其对周边环境中的雌激素贡献很小。然而,野外调查结果却表明实际情况下雌激素的迁移性高于理论期望值。因此,畜禽养殖对周边环境中雌激素的贡献量的大小尚未明确。本论文综述了畜禽养殖过程中环境雌激素的排放情况,结合国内外的调查研究,阐述了畜禽养殖产生的环境雌激素在土壤及水体中的迁移与降解行为,探讨了影响准确评估畜禽养殖排泄物对周边水体中雌激素贡献大小的因子,并提出了今后应开展原位吸附与迁移的实验,重点考虑天然有机质及抗生素等共存物质对雌激素环境行为的影响,建立综合模型来估算不同时期养殖场对周围水环境雌激素的贡献量的建议。     

Factors affecting HCH and DDT in soils around watersheds of Beijing reservoirs,China

The factors that influence the dynamics of hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) in soils around the watersheds of Beijing reservoirs were examined. Compared with other studies on HCH and DDT in soils and established reference values, the concentrations of HCH and DDT in soils around our study area were relatively low. The relationships between HCH and DDT concentrations and land use, soil texture, and soil properties were discussed. HCH and DDT concentrations were higher in arable soils than those in uncultivated fallow soils. Although land use was the most important factor affecting HCH and DDT residues, additional factors such as soil texture and soil total organic carbon were also involved in pesticide retention in soils. The results indicated that the historical agricultural applications of HCH and DDT were the major source of their residues. Atmospheric deposition, as well as long-distance transportation and inputs from surrounding weathered agricultural soils may also serve as important sources of HCH and DDT residues in the watersheds.     

极性有机物整合采样技术在监测水环境中农药的应用

明确水环境中农残的污染状况对研究其环境行为和生态风险至关重要。传统主动采样法耗能、耗力且单次采样仅获得瞬时浓度值。被动采样节能、方便且为时间加权平均浓度,利于大规模采样。极性有机物整合采样技术(polar organic chemical integrative sampler,POCIS)是针对极性有机物的被动采样技术,近年来在水环境中农药监测的运用越来越广泛。本文概述了POCIS结构、原理和校正方法,探讨了环境因素(如水流速率、温度、p H、溶解性有机质、盐度和膜污染)、化合物性质及POCIS结构对农药采样速率(Rs)的影响。此外,综述了POCIS在监测水环境中农药的应用,展望了POCIS在该领域中的问题、解决方式及前景。     

兽药抗生素对生态环境的混合毒性研究进展

抗生素是环境中普遍存在的污染物,畜牧水产养殖是其主要来源之一.环境中可能同时存在多种抗生素残留,因此单一药物的毒性评价难以反映抗生素对生态环境的影响,应探究其混合物的毒性效应.本文在总结大量文献的基础上,介绍了兽用抗生素的残留现状,总结了兽用抗生素对生态环境的混合毒性研究进展,讨论了兽用抗生素残留对土壤生物和水生生物的...     

Identification of agricultural factors for improving sustainable land resource management in northern Thailand: A case study in Chiang Mai Province

This paper aims to identify the land-use factors benefiting sustainable land management in terms of environmental conservation. For evaluating the impacts of land use on the environment, the following parameters were used: chemical fertiliser and pesticide use, land-use structure and diversity. The farmers' income, land tenure and farming scale were selected for their influence on agricultural sustainability. The analysis shows a rapid increase in use of chemical fertiliser and pesticide in the past 40 years, and an observable increase in land-use diversity. The amount of chemical fertiliser used per unit area in large-scale farming was lower than that at small scales, but large-scale farming consumes more pesticide than small-scale farming. A significant negative correlation was observed between the proportions of the holdings possessing land and the holdings using the chemical fertiliser. In order to achieve sustainable agriculture, it is necessary to manage crop systems and land use towards selecting new strains and varieties of crops and fruits with a lower demand for chemical fertiliser and a higher resistance to disease and pests, balancing large- and small-scale farming, and ensuring land tenure and economic incentives.     

Effect of commercial pesticides on plant growth-promoting activities of Burkholderia sp. strain L2 isolated from rhizosphere of Lycopersicon esculentum cultivated in agricultural soil

The in vitro study was carried out to examine the toxicity of four commercially used pesticides (phorate, mancozeb, chlorpyrifos, and endosulfan) at the recommended dose (1X) and higher field doses (1.5X, 2X, 2.5X, and 3X) on plant growth-promoting activities of Burkholderia sp. strain L2, isolated from pesticide-treated rhizosphere of Lycopersicon esculentum. At the recommended dose, level of toxicity of all the pesticides to phosphate solubilization activity and indole-3-acetic acid (IAA) production was less detrimental as compared to exceeding doses. At maximum dose rate of each pesticide, the percentage decrease in phosphate solubilization and IAA production over control was found in order of chlorpyrifos < mancozeb < endosulfan < phorate. Present study proves that Burkholderia sp. strain L2 could be used as a potential microbial inoculant in the agricultural soil having persistent pesticide residues.