四溴双酚A对土壤酶活性的影响

采用室内模拟试验方法,研究了四溴双酚A对土壤多酚氧化酶、过氧化氢酶和脱氢酶活性的影响.结果表明,四溴双酚A对土壤多酚氧化酶和过氧化氢酶有一定的激活效应,这可能是土壤微生物在受到外源四溴双酚A胁迫时产生了应激反应,通过增加多酚氧化酶和过氧化氢酶的产生量来降低四溴双酚A及其代谢、中间产物对其产生的危害;同时,四溴双酚A对土壤脱氢酶产生一定的抑制效应,表明其对土壤微生物活性具有一定的抑制作用,但在试验设置的四溴双酚A浓度范围内基本未达到显著水平(P>0.05).     

镉对鲫鱼组织转氨酶和过氧化氢酶活性的影响

当水中镉离子浓度为３２ｍｇ／Ｌ，６４ｍｇ／Ｌ时，肝胰脏，肾脏和鳃的谷丙转氨酶和谷草转氨酶活性显著降低，而过氧化氢酶活性则显著升高，对鲫鱼心脏３种酶活性的影响不明显，体外试验表明，镉能直接抑制ＧＰＴ、ＧＯＴ的活性，而对Ｃａｔａｌａｓｅ活性不产生直接影响。     

暗处理和自然光修复对菹草叶片过氧化物酶和过氧化氢酶活性的影响

以自然光为对照，在预先进行暗处理，然后进行光修复的条件下，对菹草（Potamogeton crispus）过氧化物酶（POD）和过氧化氢酶（CAT）活性及其与处理时间的关系进行了初步研究，结果表明：POD活性随着暗处理时间的延长而增强，随着光修复时间的延长而减弱；暗处理与对照相比，菹草叶片POD活性之间差异不显著；光修复与对照相比，前3天内，POD活性差异不显著，随着光修复时间的延长，POD活性出现显著差异（^＊P〉0．05）。CAT活性在暗处理和光修复中都一直低于对照值；暗处理开始2天，活性开始上升，达到最大值后下降，与对照菹草叶片CAT活性比较，前6天差异显著（^＊P〉0．05），第7天为差异极显著（^＊＊P〉0．01）；在光修复过程中，CAT活性第1天明显下降，与对照相比，除第3天表现出差异性显著（^＊P〉0．05）以外，其它均差异不显著。     

连作芋艿套作对土壤养分及酶活性的影响

针对芋艿连作障碍造成土壤环境破坏的问题,进行玉米、毛豆与芋艿套作的田间试验,通过对土壤养分、土壤酶活以及芋艿产量、品质的分析,探讨套作减缓芋艿连作障碍的可行性。试验共设置4个处理:连作芋艿、非连作芋艿、套作玉米和套作毛豆。结果表明:(1)套作可以均衡连作土壤的养分含量,套作处理平均可以比连作提升速效氮9.88%、速效钾58.21%、有机质70.36%,降低速效磷64.08%。(2)套作可以提升连作土壤酶活性,套作处理平均可以比连作提高过氧化氢酶活性23.75%、脲酶活性38.15%、蔗糖酶活性129.60%。(3)在套作土壤中,过氧化氢酶活性与速效磷、速效钾显著正相关,脲酶活性与pH、速效氮显著正相关,蔗糖酶活性与有机质、速效氮显著正相关,套作使连作土壤酶活性的影响因子向非连作土壤转化。     

Cd、Ni单一及复合污染对土壤酶活性的影响

采用外源添加重金属和露天盆栽实验研究了Cd、Ni对含羞草、三叶草根际土壤脲酶、过氧化氢酶和蔗糖酶活性的影响。结果表明,Cd、Ni单一污染条件下,低浓度的Cd、Ni对含羞草组、三叶草组的脲酶、过氧化氢酶有激活作用,高浓度的Cd、Ni对土壤脲酶、过氧化氢酶有一定的抑制作用;对蔗糖酶有较强的抑制作用。在Cd、Ni复合污染条件下,对含羞草组、三叶草组的脲酶、过氧化氢酶和蔗糖酶产生抑制作用;Cd、Ni单一及复合污染对土壤酶活性的抑制大小顺序为:脲酶>蔗糖酶>过氧化氢酶,其中土壤脲酶可以作为Cd、Ni污染的预警指标。含羞草能显著提高土壤脲酶、过氧化氢酶和蔗糖酶的活性,修复能力大于三叶草,在Cd、Ni污染修复方面有很好的应用前景。     

石油污染土壤中漆酶活性的影响因素

针对纯化酶生产成本较高且土壤中漆酶活性较低的问题,通过20 d的室内对照实验,采用ABTS分光光度法测定漆酶活性,研究Cu2+、pH、温度、碳氮比及含水率对漆酶活性的影响,结果表明5个环境因素的最优值分别是40 mg·kg-1、5.2、30 ℃、40∶1和20%。环境因素与漆酶活性的高低有关,其相关性从大到小依次为pH、温度、含水率、碳氮比和铜离子浓度。其中,pH的相关性最高,相关系数为0.956。在最优条件下,培养30 d后石油烃降解率从自然条件下的8.54%提高到18.79%,最高漆酶活性达到13.97 U·g-1。     

德兴铜矿周边地区土壤酶活性研究

采用逐步多元回归和主成分分析的方法研究了德兴铜矿周边土壤中重金属和土壤酶活性的关系.结果表明:德兴铜矿周边各功能区均受到不同程度的Cu、Cd污染,Pb、Zn未超过《土壤环境质量标准》(GB 15618--1995)二级标准;各功能区土壤酶活性有显著差别,逐步回归分析表明土壤酶活性与Cu、Zn全量、生物可利用态Cu含量有显著线性关系,而与Cd、Pb无明显相关;土壤酶活性和生物可利用态Cu呈负线性关系,而与残渣态Cu有正线性关系.主成分分析显示,土壤酶信息系统的第1、第2主成分可反映酶活性总变异的96.27%,根据第1主成分对功能区酶活性的分类结果与土壤生物可利用态Cu含量的分类结果基本一致,提示土壤酶活性指标可以反映土壤生物可利用态Cu含量.     

乙草胺对土壤微生物的影响研究

研究了乙草胺在6种不同浓度下对土壤微生物种群数量及土壤中细菌、放线菌、真菌生长速率的影响.采用密闭法测定乙草胺对土壤微生物呼吸的影响.结果表明,乙草胺对土壤微生物种群数量及土壤中细菌、放线菌、真菌生长速率均有一定的抑制作用,对土壤微生物呼吸作用具有明显的抑制作用.     

等温微量量热法研究石油污染对土壤微生物活性的影响

利用TAMⅢ等温微量量热仪研究不同浓度的石油污染对土壤微生物活性的影响。对大港油田不同石油污染程度的土壤样品（3683-5-1、西51-5、西15-14和8-13-6H-1）以及实验室配置的短时间内石油污染土壤（空白、0.5%、1.5%、2.5%和4.0%）进行了微量热检测。含油量升高,总放热量升高,生长速率常数降低,峰值功率先升高后降低,达到最大峰值功率的时间随着含油量的升高而延长。结果表明,石油污染会影响土壤微生物的活性,并且在低浓度时促进微生物的生长,石油浓度高时会抑制土壤中微生物的生长代谢。     

1,2,4-三氯苯对成年斑马鱼和幼鱼几种酶活性的影响

实验室条件下,通过1,2,4-三氯苯(1,2,4-TCB)染毒对成年斑马鱼及幼鱼体内超氧化物歧化酶(SOD)、过氧化氢酶(CAT)和碱性磷酸酶(AKP)活性进行测定和比较,从而确定1,2,4-TCB暴露对斑马鱼的毒性机制。结果发现,低质量浓度(2、4、8mg/L)1,2,4-TCB处理对SOD活性有一定的应激作用,且在第8天明显高于对照组;16mg/L 1,2,4-TCB对SOD活性明显抑制。4～10d时4mg/L处理组CAT活性与对照组呈显著差异,2、4、8mg/L处理组CAT活性随时间延长先升高后降低。各处理组AKP活性在前4d基本无显著变化,2、4mg/L处理组AKP活性在第8天与对照组呈极显著差异;16mg/L处理组AKP活性低于对照组。斑马鱼胚胎暴露1,2,4-TCB孵化第6天后,3.46mg/L处理组幼鱼蛋白质与对照组呈显著差异,其他处理组与对照组无显著差异。各处理组幼鱼体内SOD、CAT和AKP活性与对照组基本无显著变化。幼鱼比成年斑马鱼对1,2,4-TCB影响更加敏感。     

Influence of soil moisture on the sequestration of organic compounds in soil

A study was conducted as a part of continuing investigation of the effect of soil moisture on the sequestration of organic compounds aged in the soil. Here, experiments focused on the effects of moisture changes within the soil before, during, and after contaminant addition. The extractability of aged (68 d) phenanthrene was greater from soil that had been subjected to wetting and drying cycles prior to solute addition as compared to soil initially maintained at constant moisture. The recovery of phenanthrene added to moist soil was increased relative to extractability from soil that was air-dried at the time of the contaminant addition. Repeated wetting and drying of soil after the addition of atrazine or phenanthrene resulted in decreased extractability of the compounds as compared to samples maintained at constant moisture. A method for rapidly sequestering contaminants is proposed and may be useful in limiting the time required for laboratory studies involving “aged” contaminants. These data build upon the findings of earlier work from our laboratory and indicate that changes in the moisture conditions of soil can affect the availability of sequestered contaminants possibly through alterations in the structure of the natural solid.     

Macro-porosity and leaching of atrazine in tilled and orchard loamy soils

Atrazine is the most commonly detected herbicide in the groundwater. Leaching of atrazine largely depends on soil management practices. The aim of this study was to examine leaching of atrazine in tilled and orchard silty loam soils. The experimental objects included: conventionally tilled field (CT) with main tillage operations including pre-plow (10 cm) + harrowing, mouldboard ploughing (20 cm), and a 35 year-old apple orchard (OR) with a permanent sward. To determine leaching of atrazine soil columns of undisturbed structure were taken with steel cylinders of 21.5 cm diameter and 20 cm high from the depth of 0–20 cm. All columns were equilibrated at water content corresponding to field capacity (0.21 kg kg⁻¹). Atrazine suspended in distilled water was dripped uniformly onto the surface of each column. Then water was infiltrated and breakthrough times of leachates were recorded. Atrazine concentration in the leachates was determined by means of HPLC Waters. Macro-porosity and percolation rate were higher in OR than CT soil. Cumulative recovery % of the atrazine applied was 1.267% for OR and approximately one third more from the CT soil but the rate of leaching (per unit of time) was greater from the OR soil. The lower leaching under OR than CT can be due to a greater SOM and the presence of earthworm burrows with organic burrow linings that could adsorb atrazine and contribute to preferential flow allowing solutes to bypass parts whereas the greater rate of leaching due to a greater infiltration rate.The results indicate potential of management practices for minimizing atrazine leaching.     

Degradation of atrazine in mineral salts medium and soil using enrichment culture

Atrazine degrading enrichment culture was prepared by its repeated addition to an alluvial soil and its ability to degrade atrazine in mineral salts medium and soil was studied. Enrichment culture utilized atrazine as a sole source of carbon and nitrogen in mineral salts medium and degradation slowed down when sucrose and/or ammonium hydrogen phosphate were supplemented as additional source of carbon and nitrogen, respectively. Biuret was detected as the only metabolite of atrazine while deethylatrazine, deisopropyatrazine, hydroxyatrazine and cyanuric acid were never detected at any stage of degradation. Enrichment culture degraded atrazine in an alkaline alluvial soil while no degradation was observed in the acidic laterite soil. Enrichment culture was able to withstand high concentrations of atrazine (110 μg/g) in the alluvial soil as atrazine was completely degraded. Developed mixed culture has the ability to degrade atrazine and has potential application in decontamination of contaminated water and soil.     

Automated evaluation of the effect of ionic liquids on catalase activity

An automated assay for the evaluation of the influence of ionic liquids on the activity of catalase was developed. The activity and inhibition assays were implemented in a sequential injection analysis (SIA) system and intended to contribute for the estimation of the toxicity of the tested compounds. The fast developed methodology was based on the oxidation of the non-fluorescent probe amplex red, in the presence of H₂O₂, to produce resorufin, a strong fluorescent compound. Catalase activity was monitored by the decreased of the fluorescence intensity due to the consumption of H₂O₂ by the enzyme. The activity assays were performed in strictly aqueous media and in the presence of increasing concentrations of seven commercially available ionic liquids and sodium azide, a strong inhibitor of catalase. IC₅₀ values between 0.15 and 2.77 M were obtained for the tested compounds, revealing distinct inhibitory effects. This allowed us to perform some considerations about the toxicity of the tested cations and anions. The developed SIA methodology showed to be robust and exhibited good repeatability in all the assay conditions. On the other hand, it proved to be in good agreement with the actual concerns of “Green Chemistry” since it involved the consumption of less than 200 μL of reagents and the production of only 1.7 mL of effluent (per cycle) and at the same time reduced the operator exposure resulting in increased environmental and human safety.     

Long-term dynamics of the atrazine mineralization potential in surface and subsurface soil in an agricultural field as a response to atrazine applications

The dynamics of the atrazine mineralization potential in agricultural soil was studied in two soil layers (topsoil and at 35-45 cm depth) in a 3 years field trial to examine the long term response of atrazine mineralizing soil populations to atrazine application and intermittent periods without atrazine and the effect of manure treatment on those processes. In topsoil samples, ¹⁴C-atrazine mineralization lag times decreased after atrazine application and increased with increasing time after atrazine application, suggesting that atrazine application resulted into the proliferation of atrazine mineralizing microbial populations which decayed when atrazine application stopped. Decay rates appeared however much slower than growth rates. Atrazine application also resulted into the increase of the atrazine mineralization potential in deeper layers which was explained by the growth on leached atrazine as measured in soil leachates recovered from that depth. However, no decay was observed during intermittent periods without atrazine application in the deeper soil layer. atzA and trzN gene quantification confirmed partly the growth and decay of the atrazine degrading populations in the soil and suggested that especially trzN bearing populations are the dominant atrazine degrading populations in both topsoil and deeper soil. Manure treatment only improved the atrazine mineralization rate in deeper soil layers. Our results point to the importance of the atrazine application history on a field and suggests that the long term survival of atrazine degrading populations after atrazine application enables them to rapidly proliferate once atrazine is again applied.     

Evaluation of flow injection analysis method with spectrophotometric detection for the determination of atrazine in soil extracts

A method for determining atrazine in soil extracts was evaluated by flow injection analysis with spectrophotometric detection. The method is based on the reaction of atrazine with pyridine in an acid medium followed by the reaction with NaOH and sulfanilic acid. Several analytical conditions were previously studied and optimized. Under the best conditions of analysis, the limits of detection and quantification were 0.15 and 0.45 mg L^?1, respectively, for a linear response between 0.50 and 2.50 mg L^?1, and a sampling throughput of 21 determinations per hour. Using the standard addition method, the maximum relative standard deviation of 17% and recovery values between 80 and 100% were observed for three extracts from soil samples with different composition. The proposed method is simple, low-cost and easy to use, and can be employed for studies involving atrazine in soil samples or for screening of atrazine in soils.     

Continuous time random walk model better describes the tailing of atrazine transport in soil

Contaminant transport in soils is complicated and involves some physical and chemical nonequilibrium processes. In this research, the soil column displacement experiments of Cl⁻ and atrazine under different flow velocities were carried out. The data sets of Cl⁻ transport in sandy loam fitted to the convection dispersion equation (CDE) and the two-region model (TRM) indicated that the effects of physical nonequilibrium process produced by immobile water on the breakthrough curves (BTCs) of Cl⁻ and atrazine transport through the repacking soil columns were negligible. The two-site model (TSM) and the continuous time random walk (CTRW) were also used to fit atrazine transport behavior at the flow rate of 19.86 cm h⁻¹. The CTRW convincingly captured the full evolution of atrazine BTC in the soil column, especially for the part of long tailing. However, the TSM failed to characterize the tailing of atrazine BTC in the soil column. The calculated fraction of equilibrium sorption sites, F, ranging from 0.78 to 0.80 for all flow rates suggested the contribution of nonequilibrium sorption sites to the asymmetry of atrazine BTCs. Furthermore, the data sets for the flow rates of 6.68 cm h⁻¹ and 32.81 cm h⁻¹ were predicted by the TSM and the CTRW. As to the flow rate of 6.68 cm h⁻¹, the CTRW predicted the entire BTC of atrazine transport better than the TSM did. For the flow rate of 32.81 cm h⁻¹, the CTRW characterized the late part of the tail better, while the TSM failed to predict the tailings of atrazine BTC.     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

Biotransformation of atrazine and metolachlor within soil profile and changes in microbial communities

Biotransformation studies of atrazine, metolachlor and evolution of their metabolites were carried out in soils and subsoils of Northern Greece. Trace atrazine, its metabolites and metolachlor residues were detected in field soil samples 1 year after their application. The biotransformation rates of atrazine were higher in soils and subsoils of field previously exposed to atrazine (maize field sites) than in respective layers of the field margin. The DT₅₀ values of atrazine ranged from 5 to 18 d in the surface layers of the adapted soils. DT₅₀ values of atrazine increased as the soil depth increased reaching the value of 43 d in the 80-110 cm depth layer of adapted soils. Metolachlor degraded at slower rates than atrazine in surface soils, subsoils of field and field margins with the respective DT₅₀ values ranging from 56 to 72 d in surface soils and from 165 to 186 d in subsoils. Hydroxyatrazine was the most frequently detected metabolite of atrazine. The maximum concentrations of metolachlor-OXA and metolachlor-ESA were detected in the soil layers of 20-40 cm depth after 90 d of incubation. Principal Component Analysis (PCA) of soil Phospholipid Fatty Acids (PLFAs), fungal/bacterial and Gram-negative/Gram-positive ratios of the PLFA profiles revealed that the higher biotransformation rates of atrazine were simultaneously observed with the abundance of Gram-negative bacteria while the respective rates of metolachlor were observed in soil samples with abundance of fungi.     

Competitive biodegradation of dichlobenil and atrazine coexisting in soil amended with a char and citrate

The role of char nutrients in the biodegradation of coexisting dichlobenil and atrazine in a soil by their respective bacterial degraders, DDN and ADP, was evaluated. Under growing conditions, their degradation in soil extract was slow with <40% and <20% degraded within 64 h, respectively. The degradation in extracts and slurries of char-amended solids increased with increasing char content, due to nutritional stimulation on microbial activities. By supplementing soil extract with various major nutrients, the measured degradation demonstrated that P was the exclusive limiting nutrient. The reduction in the degradation of coexisting dichlobenil and atrazine resulted apparently from the competitive utilization of P by DDN and ADP. With a shorter lag phase, ADP commenced growing earlier than DDN with the advantage of utilizing P first in insufficient supply. This resulted in an inhibition on the growth of DDN and thus suppression on dichlobenil degradation.