1-Octanol/Water Partition Coefficients of 5 Pharmaceuticals from Human Medical Care: Carbamazepine, Clofibric Acid, Diclofenac, Ibuprofen, and Propyphenazone

Laboratory studies were conducted to characterize the 1-octanol/water partition coefficients of pharmaceutically active substances carbamazepine, clofibric acid, diclofenac, ibuprofen, and propyphenazone. Partition coefficients determined by shake flask experiments (OECD guideline 107) varied between log K _OW 1.51 for carbamazepine, 2.88 for clofibric acid, 1.90 for diclofenac, 2.48 for ibuprofen, and 2.02 for propyphenazone. Comparison of these values with the literature values revealed rather significant differences for most of the compounds. The partitioning coefficients of the acidic compounds diclofenac and ibuprofen agreed much better with sorption and mobility data from previously conducted experiments, whereas K _OW values for carbamazepine were lower and for clofibric acid higher than expected from experiments. Only K _OW values for propyphenazone were in the same range as reported in the literature and expected from column experiments.     

Presence of Pharmaceuticals and Hormones in Waters from Sewage Treatment Plants

This paper describes the presence of 33 pharmaceuticals and hormones in waters from two sewage treatment plants (STPs) situated in Catalonia, in northeastern Spain. The target compounds were one psychoactive stimulant, one antiepileptic, four analgesics and non-steroidal anti-inflammatories, one lipid regulators, two anti-ulcer agents, nine antibiotics (sulfonamides and macrolides), two beta-blockers, two metabolites, and 11 hormones (free and conjugates). The determination was performed using liquid chromatography coupled to tandem mass spectrometry after enrichment by solid-phase extraction with Oasis HLB sorbent. Most of the pharmaceuticals were found in both influent and effluent samples from the two STPs. The most frequently detected were caffeine, acetaminophen, carbamazepine, diclofenac, ibuprofen, naproxen, sulfamethoxazole, sulfapyridine, sulfathiazole, ranitidine, omeprazole, estrone 3-sulfate, and estradiol 17-glucuronide. Specifically, the highest concentrations found in influents were 19,850?ng/L (acetaminophen), 9,945?ng/L (caffeine), 4,215?ng/L (ibuprofen), 5,695?ng/L (sulfamethoxazole), and 5,140?ng/L (sulfathiazole). Most of the pharmaceuticals present in influent waters were found in effluents at lower concentrations. The highest concentrations in effluents were 970?ng/L (caffeine), 670?ng/L (sulfamethoxazole), 510?ng/L (bezafibrate), and 1,032?ng/L (diclofenac).     

再生水灌区地下水防污性能区划模型的建立与验证

为促进地下水水资源保护和利用,根据研究区域的特点以及地下水防污性能的影响因素,基于DRASTIC模型,选用以下6个因子：地下水水位埋深、降雨入渗补给量、表层土壤类型、包气带岩性、含水水力传导度以及土地利用类型建立了再生水灌区地下水特殊防污性能区划模型。采用地理信息系统GIS技术和内梅罗指数法,绘制研究区域地下水综合污染指数分布空间图,并且探讨了防污性能区划的验证方法以及等级划分标准。结果表明：地下水综合污染指数与研究区域的防污性能具有很好的相关性（R2=0.9591）,采用DRASTIC模型评价地下水特殊防污性能是可行的,可为再生水灌区地下水的保护以及利用规划提供重要借鉴。     

干旱区重度和轻度盐碱地包气带水分运移规律

为揭示干旱区不同灌溉模式下的包气带水分运移规律,该研究综合使用原位观测、同位素示踪和数值模拟等方法,对跨流域调水背景下,克拉玛依农业开发区重度和轻度盐碱地棉田的土壤水势、土壤含水率和土壤水同位素组成特征,包气带水量平衡以及水分运移规律进行了研究。研究表明,土壤基质势调控的滴灌模式下,重度和轻度盐碱地的灌溉入渗主要影响深度是地表以下0~150 cm,土壤含水率和土壤水势对灌溉和蒸散发动态变化的响应明显,具有前期土壤水和观测期内灌溉入渗水的混合特征。深层(重度盐碱地150~260 cm;轻度盐碱地250~350 cm)受地下水毛细作用影响,土壤水势和土壤含水率对地下水埋深动态变化的响应明显,具有前期土壤水与地下水的混合特征。轻度盐碱地中间层(150~250 cm),几乎不受灌溉入渗和地下水毛细作用的影响,土壤水势和土壤含水率处于动态平衡,主要为前期土壤水的特征。HYDRUS-1D数值模拟结果表明,深层土壤水与地下水之间存在双向交换,地下水对土壤水以补给作用为主,重度和轻度盐碱地地下水补给占包气带水分来源的比例分别为7.9%和15.0%。该灌溉模式对农业开发区地下水补给有一定的抑制作用,但观测期内区域地下水位抬升幅度在50~60 cm之间,说明存在一定的土壤次生盐渍化和地下水咸化的潜在风险。     

河套灌区井渠结合膜下滴灌土壤盐分演化规律

针对内蒙古河套灌区井渠结合的问题,基于SaltMod模型建立井灌区和渠灌区水盐均衡模型,并引入含水层侧向交换量对模型进行改进,利用隆胜井渠结合试验区15 a水盐观测资料对改进的模型进行率定和验证,采用验证后的模型分析了隆胜井渠结合区在现状条件下以及在井渠结合膜下滴灌推广实施后区域的土壤盐分演化规律。结果表明,现状条件下隆胜井渠结合区土壤盐分基本稳定,尤其是渠灌区根系层盐分基本稳定,保持在较低水平,可以在长时期内满足作物生长的需求。当推广井渠结合膜下滴灌后,井灌区的生育期灌溉定额和地下水埋深对其灌溉用地根系层土壤盐分积累的影响较小,而地下水矿化度与秋浇频率的影响较大。对于井灌区,建议采用黄河水2年1次进行秋浇压盐,可以长期将土壤全盐维持在3 g/kg以下,以满足作物生长需求。     

再生水灌溉区农田包气带及地下水中硝酸盐分布特征及来源研究

本文通过对华北平原典型再生水灌溉区(河北省石家庄洨河流域)的包气带土壤、地表水和地下水进行采样分析,对硝酸盐在多种环境介质中的来源与环境行为进行了研究,识别了再生水灌溉区地下水硝酸盐污染来源,明确了不同灌溉条件对包气带土壤中硝酸盐迁移的影响。在受到城市再生水严重影响的洨河流域,地下水中的硝酸盐浓度分布范围在4.0 mg·L?1到156.6 mg·L?1之间,已经形成了距离河道2 km、深度70 m的硝酸盐高值区域,经过计算硝酸盐的垂向扩散速率为每年1～2 m。硝酸盐与氯离子的相关性表明,城市再生水是再生水灌溉区包气带、地表水和地下水中硝酸盐的主要来源。利用Geoprobe获取利用不同灌溉水农田土壤剖面样品,研究再生水对厚包气带NO3?-N垂向分布影响,再生水灌溉区和地下水灌溉区中包气带土壤的NO3?-N的平均含量为137.0 mg·kg-1和107.7 mg·kg-1,最高含量523.2 mg·L?1和725.9 mg·L?1,分别出现1.20 m和0.85 m深度,分布规律有着明显的差别。包气带土壤硝酸盐与氯离子的相关性分析表明,再生水灌溉区土壤硝酸盐主要来源于城市再生水,而地下水灌溉区可能来源于农田氮肥。地下水年龄和硝酸盐之间关系表明,地下水中1975年以前补给的硝酸盐浓度低于1975年以后补给,地下水硝酸盐污染与包气带氮入渗的历史过程密切相关。在华北平原特殊的地质水文背景下,农田面源污染对地下水的影响有限,但再生水灌溉区地下水硝酸盐污染的风险较高。     

A Case of Hydrochemical Characterization of an Alluvial Aquifer Influenced by Human Activities

21 physico-chemical parameters have been determined in 47 groundwater samples collected in October 1994 from the alluvial aquifer of the Pisuerga river, located at the north-east of Valladolid (north-western Spain). Conventional hydrochemical methods and multivariate statistical analysis have been used to discriminate natural phenomena and pollution processes in the area. It has been demonstrated the existence of a heterogeneity in groundwater mineral contents related to anthropic actions such as irrigation, source of irrigation water and location of polluting sources. This study demonstrates the existence of two sub-units in the alluvial aquifer (left and right river banks) with different hydrochemical characteristics, and identifies three different singular areas in the left bank. Groundwater from this bank showed higher levels of dissolved ions caused by concentration processes derived from the predominant use of groundwater for crop irrigation, whilst in the right bank of the aquifer less saline water from canals is used. Degradation of groundwater quality has been observed in some areas of the left aquifer sub-unit (north, Santovenia and south-central sites) where anomalous high concentrations of sulphate, sodium, chloride and nitrate were measured, and can be related to the presence of potentially polluting sources such as leachates from industrial waste disposals, sewage effluents and use of organic and inorganic fertilizers.     

再生水加氯对滴灌系统堵塞及番茄产量与氮素吸收的影响

加氯处理是防止再生水滴灌系统生物和化学堵塞的常用方法,但有关加氯处理对作物生长影响的研究尚不充分。通过在日光温室内的田间试验,研究了加氯浓度和加氯频率对再生水滴灌灌水器堵塞特性、番茄产量和品质的影响;建立了土壤硝态氮含量随土壤电导率、含水率和温度变化的多元回归模型,分析了加氯处理对根区土壤硝态氮变化动态和氮素吸收的影响。结果表明,加氯处理能够有效防止再生水滴灌引起的灌水器流量降低;再生水滴灌增加了硝态氮在土壤表层（15 cm深度）的累积,促进了作物对氮素的吸收;加氯处理使植株吸氮量明显降低,加剧了硝态氮在土壤表层的累积,累积量随着加氯浓度和加氯频率的增大而增大;再生水滴灌的番茄产量略高于地下水滴灌,而再生水加氯处理会使产量有所降低;再生水滴灌使番茄口感指标（可溶性糖和水溶性总酸）显著提高、营养指标（Vc含量和可溶性固形物）显著降低,加氯处理能够有效缓解营养指标的降低趋势。采用浓度低于50 mg/L、频率低于两周1次的加氯处理对作物的氮素吸收有一定的抑制作用,但不会对作物生长造成明显不利影响。     

Simulation of chromium transport in the unsaturated zone for predicting contaminant entries into the groundwater

Heavy metal contaminations in the top‐soil layers can impose serious threats to groundwater quality. A seepage water prognosis of probable future contaminant entries at the groundwater surface has to take into account the emission characteristics of the source zone and the reactive transport of the contaminated leachate through the unsaturated zone. Here, a possible approach is presented, exemplarily for a site contaminated with chromium, encompassing batch elution experiments, unsaturated soil column leaching experiments with flow interruption, soil monolith lysimeter experiments, and numerical modeling of non‐equilibrium solute transport. The prognosis provides a long‐term prediction of Cr concentrations at the groundwater surface. It must be emphasized, that the modeling results are uncertain, because several of the parameters in the simulations can be determined only with significant errors. Additionally, the approach is not applicable routinely for every hazardous waste site. Our study reveals, however, that reactive contaminants can possibly reach the groundwater at hazardous concentrations within very short time.     

北京农田污水灌溉正负效应价值评价研究

采用环境经济学方法对北京市郊区农田污水灌溉的正负效应价值进行了评估。结果表明:2002年北京市农田污水灌溉的正效应价值约为4.62亿元,占当年农业增加值的9.3%,其中减少污水处理成本和节约清洁水资源的价值所占份额较大,分别为49.7%和27.6%,其次为节约化肥和粮食增产价值,分别为18.1%、3.1%;负效应价值约为1.39亿元,占当年农业增加值的2.8%,其中粮食减产造成的损失占总损失的46.5%,品质下降占2.2%,土壤污染占30.3%,人体健康损失占15.7%,而地下水污染占5.2%。污水灌溉的正负效应价值比为3.3∶1,其中污水灌溉的直接经济价值为负效应价值的1.7倍,说明污水灌溉的经济收益几乎完全是靠牺牲环境所维持的。因此必须高度重视污水灌溉造成的污染损失。     

Release and mobility of polycyclic aromatic hydrocarbons and iron‐cyanide complexes in contaminated soil

Export of organic and inorganic pollutants from the unsaturated zone of manufactured gas plant (MGP) sites may endanger groundwater quality. The release and mobility of polycyclic aromatic hydrocarbons (PAH) and iron‐cyanide complexes (FeCN) in soils from a former MGP site were studied in column and batch experiments. The unsaturated column experiment involved two parts. (1) The development of steady‐state effluent concentrations was studied under constant irrigation. (2) Rate‐limited contaminant release was studied by the system's response to flow interruption. Transport data were supplemented by a sequential batch‐desorption experiment. During constant irrigation the initial concentrations of total PAH and FeCN, but also the concentration of dissolved organic carbon (DOC) were higher than the steady state level, indicating that a specific fraction of the DOC and the contaminants was readily mobilized. Cyanide reached a constant effluent concentration after seven pore volumes (pvs), whereas equilibration of effluent PAH took 20 pvs. After flow interruption, rate‐limited release of DOC, PAH, and FeCN was observed by increased effluent concentrations. Comparison of FeCN levels with theoretical equilibrium concentrations indicated that in addition to the dissolution of iron(II)ferrocyanide (Berlin Blue), Fe₄[Fe(CN)₆]₃, other cyanide‐species may control the release and such the mobility of FeCN. This was confirmed by decreasing FeCN concentrations during sequential batch extractions. Due to rate‐limited release, seepage water concentrations of DOC, PAH, and FeCN in alkaline MGP soils are influenced by the flow regime. Experiments performed at continuous irrigation may therefore severely underestimate the release of PAH and FeCN under field conditions. The effect of DOC on the release and mobility of PAH and FeCN under transient conditions has to be further investigated.     

干旱区竖井灌排下盐分运移对地下水质的影响——以新疆哈密盆地为例

利用MODFLOW和MT3DMS软件对竖井灌排下的地下水量与水质变化趋势进行了模拟。计算结果表明,尽管这一工程措施在一定时期内可起到控制地下水位与降低表层土壤盐分作用,但从长远来看,由于水平排水的缺失,盐分从土壤表层下移到了中下层而并未被彻底地排出灌区,仍会在包气带某一层位或地下水中富集。一旦灌区的外部条件发生变化,盐分上移则会使土壤盐碱化,下移则使地下水质恶化。因此,对于竖井灌排区来说,有必要建立一套相应的监测系统,实时调控地下水开采量与水位,寻求一个即可使耕作层盐分控制在一定范围内,地下水咸化速率不致过快,同时又保持一定径流排盐作用的平衡区域,可能是今后面临的一种选择,从而将水盐自然运移规律改变后引发的生态与环境危害限制在可控范围。     

Contamination of soils and groundwater with new organic micropollutants: A review

The input of organic micro- and nanopollutants to the environment has grown in recent years. This vast class of substances is referred to as emerging micropollutants, and includes organic chemicals of industrial, agricultural, and municipal provenance. There are three main sources of emerging pollutants coming to the environment, i.e., (1) upon soil fertilization with sewage and sewage sludge; (2) soil irrigation with reclaimed wastewater and (3) due to filtration from municipal landfills of solid wastes. These pollutants contaminate soil, affect its inhabitants; they are also consumed by plants and penetrate to the groundwater. The pharmaceuticals most strongly affect the biota (microorganisms, earthworms, etc.). The response of microorganisms in the contaminated soil is controlled not only by the composition and the number of emerging pollutants but also by the geochemical environment.     

Deep infiltration through a sandy alluvial fan in semiarid Niger inferred from electrical conductivity survey,vadose zone chemistry and hydrological modelling

In semiarid southwestern Niger, most of the groundwater recharge is indirect and occurs through endoreic ponds. Elsewhere in the landscape, there is no evidence of deep infiltration, with a possible exception for gullies and alluvial fans on sandy slopes. In order to verify this hypothesis, a detailed geophysical and geochemical survey was conducted on a large, representative mid-slope fan (6 ha). At this site, distributed hydrological modelling conducted over the encompassing endoreic catchment (190 ha) showed high losses of runoff water by infiltration. Electromagnetic mapping and 2-D electrical imaging survey were used to investigate the 35 m deep vadose zone; in addition, 8 boreholes were drilled following the geophysical survey to constrain the interpretation. Variations in apparent electrical conductivity measured in boreholes appear to be mainly linked with changes in the soil solution mineralization. An extrapolation throughout the area shows that apparent electrical conductivity of the ground is systematically lower below channels; this suggests localised leaching through the unsaturated zone. A physically-based, 2-D distributed hydrologic model was used to estimate the amount of surface water loss by infiltration for the 1992–2002 period. Depending on year, infiltrated volumes range from 1000 to 24 000 m³. This represents between 5% and 16% of the runoff that reaches the final outlet of the basin, an endoreic valley bottom pond where recharge to the aquifer has been shown to occur. Because leaching of the vadose zone is observed down to a depth of 10 m below channels, episodic groundwater recharge through sandy mid-slope fans is highly probable during rainy years.     

Ammonium-nitrate dynamics in the critical zone during single irrigation events with untreated sewage effluents

Purpose

Previous studies in the Mezquital Valley evidenced that irrigation with untreated sewage effluent supplies two- to tenfold larger nitrogen doses to crops than common fertilizer recommendations. However, nitrate concentrations in the groundwater are only slightly above threshold concentrations for drinking water. To understand the N dynamics in this agroecosystem, we quantified nitrogen inputs, outputs, and transformations within the rooting zone and in the vadose zone down to the aquifer (i.e., in the critical zone).

Materials and methods

Single irrigation events were monitored in three different fields cropped with either annual rye grass (Lolium rigidum) or oats (Avena sativa L.) harvested for fodder. For each irrigation event, the total amount of water entering and leaving the field was quantified with a flowmeter. Soil pore water was collected with either microsuction cups or observation wells and groundwater was sampled at two wells. All water samples were analyzed for total nitrogen (Nt), ammonium nitrogen (NH₄ ⁺–N), nitrate nitrogen (NO₃ ^?–N), chloride (Cl^?1), and pH. Organic N was calculated as the difference between total N and inorganic N. The water tension and the soil water content were monitored before, during, and after the irrigation with tensiometers and TDR probes, respectively, installed at different depths and at three sites within each field. Batch experiments were conducted to assess the NH₄ ⁺ adsorption capacity of the soils.

Results and discussion

The irrigations added 537 to 727 kg ha^?1 N in form of organic N (40 %) and NH₄ ⁺–N (60 %) to the fields. Crops absorbed 65 % of the N and 31 to 66 kg NO₃ ^?–N ha^?1 leached out beyond the rooting zone (>40 to 130 cm). Batch experiments evidenced an ammonium adsorption capacity of 43 and 53 % of the input ammonium mass. Nitrification dominated over denitrification as the water infiltrated through the soil, evidenced by changes in nitrate concentrations and pH values in the soil pore water. The behavior of the total N/Cl ratio with depth indicated possible N losses due to NH₃ volatilization at the field surface, a temporal withdrawal of N from the soil solution due to NH₄ ⁺–N adsorption in the rooting zone, as well as probable denitrification losses in the vadose zone.

Conclusions

Although the studied agroecosystem muses the large N inputs relative efficiently, between 7 and 10 % of the added N with each irrigation leaches beyond the crop root zone as nitrate. This is triggered by overflow irrigation, since up to 8,699,000 L of water with N concentrations of up to 50 mg total N L^?1 infiltrate rapidly through macropores beyond the rooting zone. Additionally, ammonia volatilization and denitrification seem to be occurring. The latter could provide a self-cleaning potential to the system, if it reaches N₂ and needs further verification. Nevertheless, N inputs to the system should match crop uptake to avoid groundwater and atmospheric pollution.

     

Transport of primidone, carbamazepine, and sulfamethoxazole in thermally treated sediments—laboratory column experiments

Purpose

The transport behavior of human pharmaceuticals in groundwater depends on a multitude of factors such as the physico-chemical conditions in the aquifer and the organic carbon content of the sediment, and, in particular, on the redox conditions in the groundwater. This is of special interest at managed aquifer recharge sites where the occurrence of trace organics is important for drinking water production. The aim of this study was to evaluate the possibility of influencing the redox system of the aquifer in a way that optimizes the potential of managed aquifer recharge systems to reduce the amount of trace organics.

Materials and methods

Column studies were performed using natural and thermally treated sediments from an infiltration basin of the Berlin area, Germany. Special emphasis was placed on thermal treatment of the sediments to influence the total organic carbon (TOC) content in the sediment. In one experiment, the sediment was thermally pretreated at 550 °C, in two experiments the sediment was pretreated at 200 °C, and in one the sediment was untreated. Furthermore, the influence of ozonation, a very common disinfectant used in drinking water production, was studied in the experiments. The retardation and degradation parameters for primidone (PMD), carbamazepine (CBZ), and sulfamethoxazole (SMX) under different redox conditions were evaluated.

Results and discussion

Oxic conditions were obtained in the experiment with low TOC (0.06 wt%) in the sediment pre-treated at 550 °C. Anoxic conditions were predominant in two column experiments with a TOC content of 0.17 wt% in the sediment, irrespective of the mode of treatment (natural or 200 °C). All three pharmaceutical compounds show almost conservative transport behavior with retardation factors between 1.02 and 1.25 for PMD, between 1.06 and 1.37 for CBZ, and between 1.00 and 1.08 for SMX. Differences in the transport behavior were observed depending on the TOC content of the sediment. For CBZ, and to a minor extent for PMD, the higher retardation factors were observed in the sediment with a TOC content of 0.17 wt% under anoxic conditions. The ozonation of the influent water affects the influent concentrations of PMD, CBZ and SMX. However, it has no influence on the oxygen concentration of the column outflow.

Conclusions

CBZ and PMD are retarded in the presence of organic matter in the aquifer. Variations of the TOC content of the sediment have a direct influence on the retardation of CBZ and PMD. The three human pharmaceuticals may be ranked in order of decreasing retardation: CBZ?>?PMD?>?SMX. The microbial activity in the experiments was not studied, although it can be assumed that the thermal pretreatment influences the microbial activity in the sediments. In particular, the microbial activity was severely inhibited at 550 °C, resulting in a shift of the redox conditions.     

Microbial contamination of alluvial gravel aquifers by septic tank effluent

The effects of two methods of septic tank effluent disposal on the microbial quality of alluvial gravel aquifers were investigated at an experimental site in the Canterbury Plains, New Zealand. The movement of faecal coliform bacteria 9 m from a 5.5 m deep soakage pit into an unconfined aquifer, and 42 m from an 18 m deep injection bore into a confined aquifer was recorded. Partial sealing of the soakage pit sidewalls was evident, but approximately 80% of the effluent appeared to percolate rapidly into the unconfined groundwater through a permeable pathway in the unsaturated zone. There was evidence of groundwater mounding beneath the soakage pit and around the injection bore and the consequent radial spread of leachate from both disposal structures. In both the confined and unconfined aquifers, the most heavily contaminated bores exhibited marked diurnal fluctuations in faecal coliform concentrations in response to periods of effluent discharge. First arrival velocities of a rifampycin-resistantEscherichia coli tracer of approximately 15 m day^?1 in the unconfined groundwater and 151 m day^?1 in the confined groundwater were recorded. Implications of the findings for the monitoring and management of groundwater quality beneath unsewered communities on alluvial gravel formations are briefly discussed.     

热源井抽灌同井连续取/放热特性试验

针对抽灌同井连续运行特性的研究不足,利用单井循环地下换热系统砂箱试验台,以沈阳和上海2地采暖期和空调期的时间尺度为依据,分别开展了连续取热和连续放热2种运行模式下抽灌同井运行特性的试验研究。结果表明,抽灌同井在该试验条件下对取热工况更加敏感,取热比放热更为困难。在连续取热工况下,含水层在受到外界初次干扰的影响更为明显,第2个运行周期的累计取热量降幅为6个运行周期累计取热量降幅的57.1%。在热/冷负荷占优的地区,应根据建筑负荷采取辅助手段及时对含水层进行热量/冷量补给,保证热泵机组高效运行。     

铬在含水介质中的迁移及释放规律

根据天津某铬渣堆周边地区的污染情况和水文地质条件,选取该区域3种典型含水介质(黏土、粉质黏土、粉土)填充土柱,开展室内土柱淋滤实验,研究铬在含水介质中的迁移及释放规律。铬溶液淋滤实验表明,Cr(VI)在粉土中的迁移速率最快,粉质黏土中次之,黏土中最慢。清水淋滤实验表明,吸附在含水介质中的铬会在清水淋滤作用下解吸并重新释放到地下水中,从而造成地下水再次污染。根据土柱实验结果获得铬在黏土、粉质黏土和粉土中的弥散系数分别为1.87×10~(-4)m2d~(-1)、7.49×10~(-4)m2d~(-1)和1.17×10~(-4)m2d~(-1),渗透系数分别为8.60×10-6cm s~(-1)、2.14×10-5cm s~(-1)和1.34×10-5cm s~(-1),为模拟铬在含水介质中的迁移模型提供实测参数,进而为地下水中铬污染的控制与防治提供理论参考。     

Simultaneous determination of 20 pharmacologically active substances in cow's milk, goat's milk, and human breast milk by gas chromatography-mass spectrometry

This paper reports a systematic approach to the development of a method that combines continuous solid-phase extraction and gas chromatography-mass spectrometry for the simultaneous determination of 20 pharmacologically active substances including antibacterials (chloramphenicol, florfenicol, pyrimethamine, thiamphenicol), nonsteroideal anti-inflammatories (diclofenac, flunixin, ibuprofen, ketoprofen, naproxen, mefenamic acid, niflumic acid, phenylbutazone), antiseptic (triclosan), antiepileptic (carbamazepine), lipid regulator (clofibric acid), β-blockers (metoprolol, propranolol), and hormones (17α-ethinylestradiol, estrone, 17β-estradiol) in milk samples. The sample preparation procedure involves deproteination of the milk, followed by sample enrichment and cleanup by continuous solid-phase extraction. The proposed method provides a linear response over the range of 0.6-5000 ng/kg and features limits of detection from 0.2 to 1.2 ng/kg depending on the particular analyte. The method was successfully applied to the determination of pharmacologically active substance residues in food samples including whole, raw, half-skim, skim, and powdered milk from different sources (cow, goat, and human breast).