四氯乙烯和萘在氧化前后的含水层土壤上的吸附 与加标解吸研究

采用批量平衡实验法研究了四氯乙烯和萘在过氧化氢氧化前后含水层土壤上的吸附。原土经过氧化氢处理后有机质含量明显降低,但是处理前后的土样对四氯乙烯和萘的吸附差别极小。过氧化氢对原土中极性官能团的破坏使原土中的大分子有机质变为小分子的可溶性有机质离开体系,造成土壤有机质含量降低。这些具有极性官能团的大分子有机质对研究的两种化合物的吸附贡献很小。在调节液固比使各种单一体系中的液相浓度差异达到一至两个数量级的情况下,加标解吸体系下的等温线仍表现为非常规的近似水平线,说明液相浓度的降低不足以使土壤中吸附的化合物发生解吸。这一结果从另一侧面说明两种目标物在研究土壤上的吸附是以在致密有机相上的吸附为主,而这部分有机质不会被过氧化氢所氧化。因此,在评估污染土壤对地下水的危害时,需慎重使用通过吸附实验得到并基于有机质总量的分配系数。     

热活化过硫酸盐氧化污染土壤中的石油烃

石油的开采、运输、储存和使用等过程会导致一些土壤受到石油烃的污染。土壤中的石油烃会对生态安全和人类健康造成潜在危害，因此需要开展土壤修复。本研究采用热活化过硫酸钠氧化处理污染土壤中的石油烃，考察了氧化剂剂量和超声结合热活化对石油烃去除效率的影响，并对石油烃氧化产物以及氧化后土壤理化性质进行了分析。结果表明，当过硫酸钠的用量为2.4 mmol/g土壤时，石油烃的含量从3 800 mg/kg降至1 175 mg/kg，石油烃的去除效率可以达到69%。石油烃的去除效率随着氧化剂增加呈上升趋势。但当氧化剂的剂量超过2.4 mmol/g土壤时，石油烃的去除效率不再增加。使用超声结合热活化，石油烃的去除效率可以进一步提高。过硫酸盐氧化会使土壤p H显著下降，造成土壤酸化。气相色谱质谱(GC/MS)和傅里叶变换红外光谱(FTIR)分析表明石油烃氧化后可能会生成一些醇和羧酸类含氧产物。石油烃和土壤有机质被氧化成极性小分子更易进入水相，导致水中总有机碳(TOC)含量从52.4 mg/kg增加至79.8 mg/kg。扫描电镜和粒度分析表明氧化处理会改变土壤形貌，使土壤的粒径变小。氧化导致土壤的碳、氢含量减...     

不可提取态有机质对菲和萘的吸附过程的影响

土壤对疏水性有机污染物的吸附实际上是土壤中矿物和有机质两部分共同作用的结果。土壤有机质的作用相当重要，因为与矿物相比，它通常对疏水性有机污染物具有较大的热力学亲合力。因此，土壤吸附有机污染物机理的研究主要是从土壤有机质的角度进行的。土壤有机质组成复杂，主要包括非特异性有机质和腐殖质，其中腐殖质约占有机质总量的50％-80％，包括胡敏酸、富里酸和胡敏素。早期的实验研究认为疏水性有机污染物在土壤有机质相中表现为线性分配，可以用平衡分配系数来描述。但是，随着实验研究的深入，平衡分配模型不能合理解释疏水性有机污染物的一些吸附特征，如非线性吸附、溶质竞争吸附以及解吸过程的滞后现象等。后来，Weber和Huang提出土壤吸附有机污染物的三端元模型。同时Pignatello和Xing提出双模式吸附模型。都认为土壤有机质存在明显的不均匀性，并且提出了“软碳”与“硬碳”的概念。     

活化过硫酸钠氧化法修复DDTs污染场地土壤研究

本研究探讨了利用Fe2+活化过硫酸钠氧化修复长江三角洲地区某典型DDTs污染场地土壤的可行性。研究了不同因素对目标污染物去除效率的影响,包括起始pH与矿物耦合因素、过硫酸钠/Fe2+浓度比值因素和过硫酸钠浓度因素等。结果表明,当磁铁矿和赤铁矿投加到只含有过硫酸钠的泥浆体系时,在酸性和中性条件下都能显著提高DDTs的降解率(P0.01),并且pH 3.2条件时DDTs的降解率高于pH 7.7条件时的DDTs降解率;零价铁和菱铁矿因其二价铁含量较高,导致矿物近表面Fe2+过剩而消耗硫酸根自由基,进而降低了DDTs氧化效率。pH 3.2时,Fe2+/Na2S2O8的最优值为1/20,在此条件下0.16 mol/L的活化过硫酸钠反应24 h后得到DDTs最高降解率约为90%。同时还比较了活化过硫酸钠、过硫酸钠、Fenton试剂、H2O2、双氧化试剂(活化过硫酸钠与双氧水混用)和高锰酸钾6种氧化剂对DDTs氧化效果,评价了不同氧化剂的优劣之处。研究发现Fe2+活化过硫酸钠可以有效地降解DDTs的4种同系物,pH 3.2条件时6种氧化剂对DDTs的氧化降解率由大到小顺序为:活化过硫酸钠过硫酸钠Fenton试剂双氧化剂高锰酸钾H2O2。本研究结果表明活化过硫酸钠氧化法是修复DDTs污染场地土壤的有效方法,有较好的应用推广性。     

洗脱–过硫酸钠氧化联合去除土壤中PCBs的研究

考察了羟丙基-β-环糊精(HPCD)及聚氧乙烯月桂醚(Brij35)洗脱和过硫酸钠(SPS)氧化联合对模拟污染土壤以及场地污染土壤中多氯联苯(PCBs)的去除效果,探讨了洗脱时间、土液比和洗脱剂浓度对土壤中PCBs洗脱率和过硫酸钠浓度对洗脱液中PCBs降解效率的影响。结果表明:两种洗脱剂都能有效地洗脱模拟污染土壤中的2,4,4?-三氯联苯(PCB28),在土液比为1︰20,HPCD和Brij35浓度分别为20 g/L和8.0 g/L时,洗脱4 h后,土壤中PCB28的洗脱率分别可达90%和79%;用100 g/L的SPS氧化24 h后,PCB28的最大去除率分别可达90%和92%。将PCB28模拟污染土壤洗脱-过硫酸钠氧化的优化条件用于去除场地污染土壤中的PCBs(总浓度约1 400 mg/kg),发现HPCD和Brij35对PCBs的总洗脱率分别为66%和53%;SPS处理后,两种洗脱液中PCBs(10.6 mg/L)的总降解率分别为41%和52%。由此,洗脱-过硫酸钠氧化法能快速有效去除污染土壤中的PCBs,为PCBs场地污染土壤修复提供了一种新的方法。     

洗脱–过硫酸钠氧化联合去除土壤中PCBs的研究

本文考察了羟丙基-β-环糊精（HPCD）及聚氧乙烯月桂醚（Brij35）洗脱和过硫酸钠（SPS）氧化联合对模拟污染土壤以及场地污染土壤中多氯联苯（PCBs）的去除效果,探讨了洗脱时间、土液比和洗脱剂浓度对土壤中PCBs洗脱率和过硫酸钠浓度对洗脱液中PCBs降解效率的影响。结果表明,两种洗脱剂都能有效地洗脱模拟污染土壤中的2,4,4?-三氯联苯（PCB28）,在土液比为1:20,HPCD和Brij35浓度分别为20 g/L和8.0 g/L时,洗脱4 h后,土壤中PCB28的洗脱率分别可达90%和79%;用100 g/L的SPS氧化24 h后,PCB28的最大去除率分别可达90%和92%。将PCB28模拟污染土壤洗脱-过硫酸钠氧化的优化条件用于去除场地污染土壤中的PCBs（总浓度~ 1400 mg/kg）,发现HPCD和Brij35对PCBs的总洗脱率分别为66%和53%;过硫酸钠处理后,两种洗脱液中PCBs（10.6 mg/L）的总降解率分别为41%和52%。以上研究表明洗脱-过硫酸钠氧化法能快速有效去除污染土壤中的PCBs,为PCBs场地污染土壤修复提供了一种新的方法。     

加热气氛对柴油污染土壤低温热处理的影响

在N_2、CO_2、空气3种气氛条件下对柴油污染土壤进行250℃低温热处理,研究3种气氛对石油烃去除率、土壤碳/氮含量以及土壤中挥发/半挥发性有机污染物组分的影响。结果表明:在3种气氛条件下,柴油污染土壤中的石油烃总量去除率均超过98%,达到国家相关土壤质量环境标准。柴油污染土壤经过低温热处理后,污染物在土壤表层产生焦炭膜,使得热处理后的土壤保留较稳定的碳含量。土壤中的铵态氮和硝态氮受气氛影响较大,N_2条件下低温热处理后土壤中铵态氮和硝态氮含量大幅增加,而空气和CO_2条件下相对减少。柴油污染土壤中的挥发性有机污染物,经3种气氛条件下低温热处理后,大部分均被去除,仅CO_2气氛下残余少量苯系物;柴油污染土壤在热处理后有少量萘、菲等低分子量多环芳烃生成,在250℃温度下可能有产生低分子量多环芳烃的风险。综上所述,低温热处理是修复柴油污染土壤高效、可行的方法。     

高锰酸钾氧化修复污染土壤中菲和芘的研究

利用人工污染土壤,研究了高锰酸钾对4种不同土壤中菲和芘的氧化修复效果。结果表明,当高锰酸钾浓度为33.33mmol·L^-1时,土壤中菲和芘的氧化去除率达到最大。高锰酸钾氧化去除率不仅与高锰酸钾浓度有关,还与土壤性质和老化时间有关。土壤有机质含量的增加会降低高锰酸钾对土壤中菲和芘的氧化去除率;随着老化时间的增加,高锰酸钾的氧化去除率逐渐降低。老化40d后,4种土壤中菲和芘的氧化去除率显著降低,菲的氧化去除率在14%～67%之间,芘的氧化去除率在61%～84%之间。高锰酸钾氧化前后,4种土壤中有机质含量下降范围为0.77%～9.21%。从土壤有机质含量来看,高锰酸钾氧化修复多环芳烃污染土壤对土壤质量影响较小,具有较好的应用前景。     

BS-12+DAS复配修饰膨润土对苯酚、菲的不同吸附模式和机理

为探究阴离子型表面修饰剂对两性修饰膨润土吸附不同类型有机污染物的影响,采用阴离子型表面修饰剂正十烷基磺酸钠(DAS)对两性修饰剂十二烷基二甲基甜菜碱(BS-12)修饰膨润土进行复配修饰,恒温浸泡处理法研究复配修饰膨润土对疏水性不同的有机污染物苯酚和菲的吸附模式差异及原因,并对比了不同温度、pH和离子强度条件下供试土样吸附苯酚及菲的吸附量及表观热力学参数。结果表明:BS+DAS复配修饰土样对苯酚及菲的吸附量随DAS修饰比例的增大而减小,且苯酚吸附量变化更为显著,复配修饰土样对苯酚的吸附模式为"无限"型分配吸附,对菲为"有限"型分配吸附;供试土样对苯酚及菲的吸附均为物理吸附,呈现增温负效应;pH升高促进了供试土样对苯酚的吸附,抑制了菲的吸附;离子强度在0.001~0.1 mol L~(-1)范围内,可促进供试土样对苯酚及菲的吸附;热力学参数结果表明,BS+DAS两性复配修饰膨润土对苯酚及菲的吸附是自发的物理吸附过程,DAS增大了土样表面正辛醇/水分配系数的对数(logP),造成了苯酚及菲吸附模式的不同,结果证实,以化学修饰方式增强土样有机碳含量以增加对不同疏水性有机污染物的吸附,不但要考虑有机碳含量的影响,同时也要考虑土样表面有机相和污染物之间"相溶性"的差异。     

挥发性有机污染物在土壤中的运移机制与模型

挥发性有机污染物在土壤多孔介质中有三种可能的存在状态：溶于水中、挥发为气体及吸附于固体颗粒。挥发性有机污染物在水、气、固体颗粒三相间的物质交换与分配是决定其运移的重要因素，在相间物质交换为平衡的条件下，可用阻滞系数来表示其影响，污染物与土壤固体颗粒间的非平衡吸附解吸是相间交换中影响污染物运移的最重要的机制，由于天然土壤具有固有的不均质性，必须用多个反应系数才能准确描述污染物与固体颗粒间的非平衡吸附解吸。     

Partitioning of polycyclic aromatic hydrocarbons (PAH) to water-soluble soil organic matter

The mobility of polycyclic aromatic hydrocarbons (PAH) in soils can be influenced by the presence of dissolved organic matter. Partition coefficients of selected polycyclic aromatic hydrocarbons, ranging from 3-ring to 6-ring compounds, to water-soluble soil organic matter (WSSOM) were determined. Partition coefficients were determined for WSSOM obtained from two soils under agricultural use and forest and for commercially available humic acid (Aldrich), taking advantage of a reversed phase (C₁₈) separation method. The WSSOM was characterised with regard to charge and hydrophilic/hydrophobic properties with a dissolved organic matter (DOM) fractionation method. No sorption to WSSOM was found for the tri- and tetracyclic PAH, whereas the penta- and hexacyclic PAH showed a significant binding to both types of WSSOM and to Aldrich humic acid. The affinity of penta- and hexacyclic PAH to WSSOM was considerably lower compared to the affinity to Aldrich humic acid. This is suggested to be due to the lower amount of hydrophobic fractions, c. 30%, in the natural WSSOM as compared to Aldrich humic acid. Effective partition coefficients (Koc_eff) for the sorption of PAH to bulk soil calculated from K_DOC and DOM in the naturally occurring concentration range were only 60–70% of the K_oc values in pure water. The impact of DOM on pollutant transport is further influenced by non-equilibrium behaviour of PAH in soils and by sorption of DOM to the solid-soil matrix. Several scenarios are described in which the effect of DOM on pollutant transport may become important.     

土壤主要理化性质对湘粤污染农田镉稳定效果的影响

利用盆栽试验研究了稳定剂(石灰、海泡石联合施用)对湖南、广东两省区不同性质土壤上生长的小青菜(Brassica chinensis L.)生物量、重金属吸收以及土壤pH和重金属提取态含量的影响,探讨了影响镉(Cd)稳定修复效果的土壤性质参数。结果表明:施加稳定剂对增加酸性土壤上小青菜生物量效果显著,土壤pH、有机质(OM)、全量Cd和黏粒是影响小青菜生物量变化的主要因素;土壤pH、阳离子交换量(CEC)、OM、黏粒是影响小青菜Cd含量变化的主要因素;土壤pH、CEC、全量Cd和黏粒是影响土壤提取态Cd含量变化的主要因素。     

Sorption of s-Triazine Herbicides in Organic Matter Amended Soils: Fresh and Incubated Systems

Fresh amendment of soil with sewage sludge and composted sewage sludge resulted in increased sorption of three s-triazine herbicides: atrazine, ametryn and terbuthylazine. The extent of increased sorption (as evaluated by sorption coefficients K_d or K_f) was a function of soil type, such that sorption in amended organic carbon-poor soil (0.4% OC) was more enhanced than in amended organic carbon-rich soil (1.55% OC). Despite significant differences between the organic amendments in terms of humic and fulvic acid content, humin content, soluble organic matter content, total organic matter content, and H/C and O/C atomic ratios, organic matter composition had no discernible effect on either sorption distribution coefficients or on isotherm linearity in amended soils. Soils amended with composted sludge had the same sorption potential as did soils amended with the analogous uncomposted sludge. After incubating soil-sludge mixtures for a year at room temperature, organic matter content decreased to original pre-amendment levels. Sorption coefficients for the three compounds similarly decreased to initial pre-amendment values. Organic carbon normalized sorption coefficients (K_oc) were essentially identical in the soils, amended soils, and incubated amended soils, indicating that sludge and compost derived organic matter does not have a significantly different sorption capacity as compared with the original soils, despite compositional differences.     

Effects of Organic Matter-Rich Amendments on Selenium Mobility in Soils

Soil organic matter (SOM) plays an important role in the Se dynamics in soil. The potential effects of vermicompost and digestate as important sources of SOM on selenium (Se) mobility were assessed in this study. Three soils differing in their physicochemical parameters, fluvisol, chernozem, and luvisol, were chosen, and three types of vermicomposts based on various bio-waste materials as digestate (vermicompost 1), kitchen waste with woodchips (vermicompost 2), and garden bio-waste (vermicompost 3) were used due to their high organic matter content. Additionally, digestate samples alone were applied. To evaluate the potential effect of vermicompost application on sorption characteristics of soils, batch sorption experiments were performed. The results showed a predominant effect on Se species in the soils, where selenite sorbed more intensively compared to selenate, regardless of the soil and ameliorative material applied. In the control, the soil sorption ability of selenite tended to decrease in the order:fluvisol > luvisol > chernozem. However, these differences were not significant. Moreover, the effects of the ameliorative materials depended on both soil and amendment used. In fluvisol, all the amendment applications resulted in a decrease in distribution coefficient (K_d values) of Se, whereas in chernozem, this effect was observed only for the digestate-based vermicompost 1. Increasing K_d levels were reported in luvisol treated with digestate; the application of garden bio-waste-based vermicompost 3 tended to decrease the K_d values. Further studies are required on long-term effects of these amendments on Se mobility in soils and the role of individual organic matter fractions in this context.     

Competitive sorption of linear alkylbenzene sulfonate (LAS) surfactants and the antibiotics sulfamethoxazole and ciprofloxacin in wastewater-irrigated soils of the Mezquital Valley,Mexico

Purpose

The increasing reuse of wastewater for irrigation introduces surfactants and antibiotics into the environment. How these two kinds of compounds interact with regard to their sorption processes in soil is not clear.

Materials and methods

We performed batch experiments to investigate the sorption of linear alkylbenzene sulfonates (LAS) and its effect on sorption of sulfamethoxazole and ciprofloxacin in irrigated and non-irrigated soils with different organic matter (OM) contents.

Results and discussion

LAS sorption was non-linear in the presence of the antibiotics, and as general trend, it increased with rising OM content of soils. Free LAS was also removed from solution by complexation with Ca²⁺. Dissolved organic compounds released from soils with OM contents ≥18.4 g kg^?1 further reduced LAS sorption. Sorption of sulfamethoxazole was reduced by LAS sorption only in one soil with a small OM content of 9.5 g kg^?1.

Conclusions

The strong sorption of ciprofloxacin is not affected by LAS. Sulfamethoxazole sorption only competes with LAS sorption in organic matter-poor soils. Accumulation of organic matter in soils, for example due to long-term wastewater irrigation, provides extra sorption capacity for LAS and sulfamethoxazole so that competition for sorption sites is reduced.

     

Stabilization of dissolved organic matter by sorption to the mineral soil

The main process by which dissolved organic matter (DOM) is retained in forest soils is likely to be sorption in the mineral horizons that adds to stabilized organic matter (OM) pools. The objectives of this study were to determine the extent of degradation of sorbed OM and to investigate changes in its composition during degradation. DOM of different origins was sorbed to a subsoil and incubated for 1 year. We quantified mineralized C by frequent CO₂ measurements in the headspace of the incubation vessels and calculated mean residence times by a double exponential model. Mineralization of C of the corresponding DOM in solution was used as a control to estimate the extent of DOM stabilization by sorption. Changes in the composition of sorbed OM during the incubation were studied by spectroscopic (UV, fluorescence) and isotope (¹³C, ¹⁴C) measurements after hot-water extraction of OM.The fraction of sorbed organic C mineralized during the incubation was only one-third to one-sixth of that mineralized in solution. The mean residence time of the most stable OM sample was estimated to increase from 28 years in solution to 91 years after sorption. For highly degradable DOM samples, the portion of stable C calculated by a double exponential model nearly doubled upon sorption. With less degradable DOM the stability increased by only 20% after sorption. Therefore, the increase in stability due to sorption is large for labile DOM high in carbohydrates and relatively small for stable DOM high in aromatic and complex molecules. Nevertheless, in terms of stability the rank order of OM types after sorption was the same as in solution. Furthermore, the extent of sorption of recalcitrant compounds was much larger than sorption of labile compounds. Thus, sorptive stabilization of this stable DOM sample was four times larger than for the labile ones. We conclude that stabilization of OM by sorption depends on the intrinsic stability of organic compounds sorbed. We propose that the main stabilization processes are selective sorption of intrinsically stable compounds and strong chemical bonds to the mineral soil and/or a physical inaccessibility of OM to microorganisms. The UV, fluorescence and ¹³C measurements indicated that aromatic and complex compounds, probably derived from lignin, were preferentially stabilized by sorption of DOM. The ¹³C and ¹⁴C data showed that degradation of the indigenous OM in the mineral soil decreased after sorption of DOM. We estimated DOM sorption stabilizes about 24 Mg C ha⁻¹ highlighting the importance of sorption for accumulation and preservation of OM in soil.     

长期施肥对我国典型土壤活性有机质及碳库管理指数的影响

对我国重点农区的6种典型土壤红壤、灰漠土、垆土、潮土、褐土、黑土长期耕作施肥后的活性有机质及碳库管理指数(CMI)进行了研究,探讨施肥对不同土壤活性有机质和CMI的影响。土壤活性有机质用KMnO4氧化法测定,采用3种浓度KMnO4(33、1673、33.mmol/L)将土壤活性有机质分为高活性有机质、中活性有机质和活性有机质3部分。结果表明,只耕作不施肥(CK)10年后土壤活性有机质含量降低,CMI下降11.1～63.6,其中垆土、褐土下降幅度最大、黑土最小。施用化肥也使土壤活性有机质下降,其中单施氮(N)的潮土活性有机质下降最大,达31.3%;化肥配合施用(NPK)的红壤活性有机质下降最大,其余土壤相对较小。施肥使土壤活性有机质和总有机质含量增加,高于初始土壤和CK。施用有机肥或有机肥配施化肥,土壤活性有机质含量和CMI均显著增加,CMI以红壤上升最大,达91.4,潮土最小,仅为4.6。土壤活性有机质的数量及CMI变幅大于土壤总有机质的变化幅度,以CMI变化为大,说明CMI是评价施肥耕作对土壤质量影响的最好指标。土壤活性有机质分组结果表明,红壤活性有机质组成以高活性有机质为主;垆土、灰漠土活性有机质以高活性和中活性两部分为主;潮土以中活性有机质为主。施肥对红壤、灰漠土活性有机质组分影响明显,对垆土、潮土影响相对较小。     

连续种植蔬菜对潮土磷素水平的影响

Soil P status, inorganic P fractions, and P sorption properties were studied using sandy fluvo-aquic horticultural soils, which are high in organic matter content for vegetable production in comparison with a soil used for grain crop production in Zhengzhou, Henan Province, China. P fractions, Olsen-P, and OM were determined at different depths in the soil profile and sorption isotherm experiments were performed. Most P in excess of plant requirements accumulated in the topsoil and decreased with soil depth. Total P, inorganic P, and OM concentrations increased with continued horticultural use. Olsen-P concentrations in the 0-20 cm depth of horticultural soils were 9 to 25 times higher than those of the grain crop soil. A linear transformation of the Langmuir equation showed that the P adsorption maximum (491.3 mg P kg^-1) and the maximum phosphate buffering capacity (162.1 L kg^-1) for 80-100 cm were greater in the grain crop soil than the horticultural soils. Thus, the most immediate concern with excess P were in areas where heavy P fertilizer was used for vegetable crops and where soil P sorption capacities were low due to sandy soils and high organic matter content.     

Effect of soil pH on the sorption capacity of soil organic matter for polycyclic aromatic hydrocarbons in unsaturated soils

Sorption by soil organic matter (SOM) is considered the most important process affecting the bioavailability of hydrophobic organic chemicals (HOCs)in soil.The sorption capacity of SOM for HOCs is affected by many environmental factors.In this study,we investigated the effects of soil pH and water saturation level on HOC sorption capacity of SOM using batch sorption experiments.Values of soil organic carbon-water partition coefficient (K_OC) of six selected polycyclic aromatic hydrocar...