Tracing Pharmaceuticals in the Unsaturated Zone (10 pp)

Background, Aim and Scope   One of the first occurrences of pharmaceutically active compounds in groundwater was reported from the sewage irrigation farms south of Berlin. At these sewage irrigation farms treated sewage effluent passed the soil and unsaturated zone before reaching the aquifer. Clofibric acid was detected in pore water from soils of those sewage irrigation farms in concentrations between 65 ng/L and 1430 ng/L. The aim of this study was to investigate the transport behavior of regularly detected clofibric acid, diclofenac, ibuprofen, and propyphenazone under conditions comparable to those at the sewage irrigation farms in a multiple compound sand column laboratory experiment. Materials and Methods   Sediment column experiments were conducted to study the transport of pharmaceuticals in the unsaturated zone. The migration was measured in fine to medium grained sand and leaching solution containing 1 mg/L of pharmaceutically active compounds and 61 mg/L of the tracer lithium chloride (LiCl). For the analysis of the pharmaceutical compounds the water samples were adjusted to a pH value of 2 and then extracted by solid-phase extraction (SPE). Before extraction, the samples were spiked with a surrogate standard for analytical quality control. The sample extracts were analyzed by capillary gas chromatography-mass spectrometry (GC-MS) with selected ion monitoring (SIM). Depending on the sample volume (100 to 200 mL) and the matrix, the limits of detection were between 1 and 10 ng/L, and the limits of quantitation were between 5 and 25 ng/L. Analysis for calcium, magnesium and lithium were carried out using a 'Trace Scan' ICP-AES from Thermo Jarrel Ash. Sodium, potassium, iron and manganese were analyzed using a Philips PU 9400 flame AAS. Analysis of anions was performed on a Dionex ion chromatograph DX 120. Results   At the sewage irrigation farms the average concentrations of clofibric acid in the unsaturated zone declined from higher values near ground surface (480 ng/L) to lower values near the groundwater table (65 ng/L). From the pharmaceuticals analyzed only clofibric acid, primidone and propyphenazone could be analyzed in the first (upper) aquifer at the sewage irrigation farms. All other pharmaceuticals could neither be detected in the first aquifer nor in the deeper aquifers. Breakthrough curves from soil column experiments revealed no transformation and no retardation for clofibric acid, whereas transformation of diclofenac was so high (79%) that no retardation factor could be calculated. Ibuprofen was significantly transformed (37%), transformation of propyphenazone (17%) was quite low and retardation (Rf = 2.05) was in the range of previously conducted column experiments. Discussion   The results confirm previously conducted experiments with clofibric acid where this compound was identified as highly mobile and persistent. The results that diclofenac and ibuprofen are significantly transformed where unexpected as other studies exhibited much lower transformation under saturated conditions at least for diclofenac. However, lower pH values and higher oxygen contents in the unsaturated zone compared to the aquifer may explain this observed high transformation of these compounds at the column experiments. Conclusions   We conclude that irrigation with sewage effluent containing the compounds used in our experiments will lead to an input into groundwater of clofibric acid, whereas diclofenac and ibuprofen will most likely be transformed during the passage. Propyphenazone will be retarded but will most likely occur in groundwater. These results from the column experiments coincide very well with the occurrence of the pharmaceuticals clofibric acid, primidone, and propyphenazone in the first aquifer. Recommendations and Perspective  : The results underline the need to study the sorption of pharmaceuticals on various materials. e.g. organic matter, surfaces at pH values occurring in the unsaturated zone. Future field studies will also include the investigation of desorption behavior in the unsaturated zone.     

Toxicity of cadmium and its competition with mineral nutrients for uptake by plants: A review

Cadmium(Cd)is a toxic heavy metal occurring in the environment naturally and is also generated through various anthropogenic sources and acts as a pollutant.Human health is affected by Cd pollution in farmland soils because food is the main source of Cd intake in the non-smoking population.For crops,Cd toxicity may result from a disturbance in uptake and translocation of mineral nutrients and disturbance in plant metabolism,inhibiting plant growth and development.However,plants have Cd tolerance mechanisms,including restricted Cd uptake,decreased Cd root-to-shoot translocation,enhanced antioxidant enzyme activities,and increased production of phytochelatins.Furthermore,optimal supply of mineral nutrients is one of the strategies to alleviate the damaging effects of Cd on plants and to avoid its entry into the food chain.The emerging molecular knowledge contributes to understanding Cd uptake,translocation,and remobilization in plants.In this review,Cd toxicity and tolerance mechanisms,agricultural practices to minimize Cd accumulation,Cd competition with essential elements(calcium,copper,iron,zinc,and manganese),and genes associated with Cd uptake are discussed in detail,especially regarding how these mineral nutrients and genes play a role in decreasing Cd uptake and accumulation in crop plants.     

Impacts of Municipal Wastewater on The Transport Characteristics of Reactive Solutes Through Agricultural Soils

Reliable transport parameters of agrochemicals and soluble pollutants are crucial for modeling and management of soil and groundwater quality. This study investigated impacts of municipal wastewater on the transport parameters of five heavy metal/metalloid compounds (NaAsO₂, Cd(NO₃)₂, Pb(NO₃)₂, Ni(NO₃)₂ & ZnCl₂), two pesticides (cartap & carbendazim) and an inert salt (CaCl₂) in four agricultural soils of Bangladesh. Solute-breakthrough concentrations were measured in repacked soil columns with time-domain reflectometry (TDR) both before and after wastewater treatment. Transport velocity (V), dispersion coefficient (D), dispersivity (λ) and retardation factor (R) of the solutes, and pertinent soil properties were determined. Wastewater reduced bulk density (γ) of the soils (from 1.32–1.37 g/cm³ to 1.26–1.35 g/cm³) by increasing organic carbon (OC) (from 0.37%–0.84% to 0.40–0.93%), increased pore-size distribution index (n) (by 0.02 unit) and reduced soil pH (from 6.32–7.45 to 5.92–6.46). D and λ decreased while V and R increased after wastewater treatment; D decreased and R increased linearly with decreasing bulk density. The correlations of V, D, and R with n improved significantly (p < 0.05) after wastewater treatment. The correlation between λ and OC improved markedly for Ca, Pb, Ni, and cartap. The observed indicative results have practical implications in developing pedo-transfer functions for solute-transport parameters using basic soil properties, which are subject to progressive modification due to agrochemicals application and wastewater irrigation.     

流域输沙函数应用的尺度限制

阐述了在流域产沙预测模型研究中,将试验水平范围的输沙函数的运用范围扩大,产生了数据来源的不确定性或错误的原因在于:模型不完善、重要过程的省略、初始条件的缺乏、初始条件的敏感度、异质性问题、外部动力等。数据来源的不确定性在小尺度、短时间内是能够控制的。大尺度的异质性是使得输沙函数不能仅仅建立在数量化的基础上,而应是系统历史的函数。因此,大尺度的流域产沙模型必须建立在突变量的发现及其相应的动力特征基础上,而不应是试验模型按比例放大。     

SWAT模拟耕作方式与盐分对区域土壤氮运移及作物产量影响

耕作方式与土壤盐渍化是影响河套灌区氮素流失及作物产量的重要因素。明确不同耕作方式与盐渍化水平下硝态氮运移量及作物产量的变化,可为制定合理的灌区耕作措施及盐渍化治理方案提供理论依据,对于揭示灌区氮素流失控制及不同作物增产潜力具有重要意义。该研究基于验证后的SWAT（Soil and Water Assessment Tool）模型,以河套灌区2种主要土壤类型为研究对象,设置不耕作（指不添加耕作管理,CK）、免耕（T1）、少耕（T2）、常规春耕（T3）和模板犁（T4）5种耕作处理,非盐化土（S1）、轻度（S2）、中度（S3）、重度（S4）4种盐分水平,研究耕作方式与土壤盐分对灌区产水量、作物吸氮量、硝态氮淋溶量及运移量、作物产量的影响。结果表明：耕作方式与土壤盐分对区域总产水量、作物吸氮量、硝态氮淋溶量、硝态氮运移及作物产量均有显著影响（P<0.05）。其中,区域产水量、硝态氮淋溶量、不同水文路径（地表、侧向和地下径流）硝态氮运移量及小麦产量均随耕作混合深度与混合效率的增加逐渐减少;作物吸氮量、玉米与葵花产量均随耕作混合深度与混合效率的增加逐渐增加。与CK相比,模板犁耕作作物吸氮量平均增加11.78%,硝态氮淋溶量平均减少16.5%,有效降低了土壤养分流失和地下水污染。增加土壤盐分通过降低土壤层有效持水量,显著增加了区域总产水量、硝态氮淋溶量（草甸盐土除外）及硝态氮地下运移量,减少了作物吸氮量和作物产量。与非盐化土相比,重度盐化土处理小麦、玉米、葵花产量平均显著减少19.15%、27.31%、26%（P<0.05）。增加土壤盐分相比转变耕作方式更能影响区域产水量、土壤养分和作物产量。因此,为更好解决灌区污染严重和作物产量下降等问题,仍需将区域土壤盐渍化防控与治理放在首要位置。     

Methane emissions from stems of Fraxinus mandshurica var. japonica trees in a floodplain forest

We measured methane (CH₄) emissions from the stem surfaces of mature Fraxinus mandshurica var. japonica trees in a floodplain forest. Flux measurements were conducted almost monthly from May to October 2005, and positive CH₄ fluxes were detected throughout the study period, including the leafless season. The mean CH₄ flux was 176 and 97 μg CH₄ m⁻² h⁻¹ at the lower (15 cm above the ground) and upper (70 cm above the ground) stem positions, respectively. The CH₄ concentration was lower in soil gas than in ambient air to a depth of at least 40 cm. One possible source of CH₄ emitted from the stems might be the dissolved CH₄ in groundwater; maximum concentrations were 10,000 times higher than atmospheric CH₄ concentrations. Our results suggest that CH₄ transport from the submerged soil layer to the atmosphere may occur through internal air spaces in tree bodies.     

土壤溶质迁移的指数函数模型

边界层方法是描述土壤溶质迁移的简单方法,通过边界层距离与时间的关系可以估计溶质迁移参数。基于边界层方法,研究了土壤溶质迁移的数学模拟及相应参数估计问题。假定土壤溶质浓度剖面为指数函数,得到了描述溶质浓度分布的指数函数模型。各参数对边界层距离的影响分析表明,应选取较小的孔隙水流速度、短历时推求土壤溶质迁移参数;对不同模型预测土壤溶质分布进行比较,结果表明,在短距离处指数型解与精确解的误差比其它都要小。误差分析表明了指数函数模型的有效性和实用性。     

考虑水迁移率动态变化改进土壤溶质地表流失模型

农田土壤溶质的地表径流流失是农业面源污染的重要组成部分,为了更加有效预测和控制农田土壤溶质的流失,该文将水迁移率考虑为随土壤侵蚀变化而变化的函数,并修改Hydrus-1D代码数值求解土壤溶质的地表径流浓度值。利用两组已经发表的试验数据对改进的模型进行校验,研究结果表明该文模拟值与观测数据的相关系数r≥0.81,残差绝对均值和均方根差与原模型的模拟值相比,分别平均减少了35.42和60.77 mg/L,该文改进的模型能更好地模拟土壤溶质的地表径流流失规律。该文的研究成果将为实际预防和控制农业面源污染提供参考。     

不同积累型苋菜(Amaranthus mangostanus L.)镉吸收转运特征差异性研究

【目的】比较高积累型苋菜品种Tianxingmi与低积累型苋菜品种Zibeixian在Cd胁迫下Cd吸收转运特征差异性,揭示苋菜品种Tianxingmi高积累镉的机理。【方法】采用水培试验,添加代谢抑制剂来研究两品种苋菜根系吸收Cd的主要途径。分别在30 μmol/L CdCl₂处理4 h、8 h、16 h、1 d和2 d采样测定,采用非损伤微测技术（Non-invasive micro-test technique,NMT）,进行植物活体动态测试,调查、测量两品种苋菜根系Cd2+离子流特征,比较了两品种对代谢抑制剂的反应。【结果】在30 μmol/L CdCl₂处理1 d后,Tianxingmi生物量达到最大值5.90 g/plant,是Zibeixian生物量的二倍;Tianxingmi根、茎和叶中Cd浓度分别为609、254和62.3 mg/kg,分别是Zibeixian的1.4倍、1.9倍和1.6倍,地上部和全株的Cd累积量分别高达602.0、1308 μg/plant;Tianxingmi富集系数（BCF）与转运系数（TF）分别为Zibeixian的2.1倍和1.5倍,这些结果两品种均表现出显著性差异（P < 0.05）。NMT技术测定两品种根系Cd2+离子流,通过扫描位点测定发现,距根尖0~300 μm范围内两品种苋菜根系Cd2+内流最强且差别最大,并在此做定点位点测定,发现Tianxingmi根系Cd2+内流是Zibeixian根系Cd2+内流的3.75倍,说明了两品种的富集特征与NMT结果一致。添加代谢抑制剂处理显著降低了高积累型Tianxingmi各器官中的Cd浓度,富集系数（BCF）与转运系数（TF）,以及根系Cd2+内流（P < 0.05）,主动吸收特征明显,而对低积累型Zibeixian的相关生理指标影响不大。【结论】两苋菜品种Cd吸收转运特征均表现出显著性差异。Tianxingmi具有更强的Cd吸收和向地上部转运与累积能力,并且根系对Cd的吸收与转运是主动需能的过程,共质体途径在Cd进入Tianxingmi根系并向地上部运输的过程中起着主要作用。     

基于COMSOL软件的绿洲盐渍化土壤中多离子耦合运移模型构建

了解盐分离子在土壤中的迁移规律可以为盐渍土的综合治理以及高效利用提供科学依据,在COMSOL多孔介质和地下水流模块模拟非饱和土壤水流的基础上,自定义偏微分方程组构建盐渍化土壤SO42–、Ca2+、Na+、Cl–、Mg2+耦合运移模型,考虑阳离子交换过程以及硫酸钙的沉淀溶解反应,并通过新疆绿洲膜下滴灌田间试验对模型进行检验,对比不同活度系数估算方法对模拟结果的影响。结果表明,各离子模拟值与实测值吻合较好,平均相对误差介于9.15%~28.57%,决定系数介于0.41~0.88,该模型能够较好地反映土壤中盐分离子的动态变化规律;在膜下滴灌条件下,膜下0~40 cm土层的盐分离子有不同程度的淋洗,Cl–和Na+的淋洗效果好于Ca2+和SO42–;活度系数的估算对模拟结果的准确性有重要影响,尤其是盐分含量较高时,采用通用的函数关系可能会带来较大的模拟误差。