基于GWLF模型的于桥水库入库河流水文模拟及氮磷负荷估算

流域模型技术应用是当前开展面源污染防治的重要工具,而水文过程的准确模拟是进行污染负荷估算的首要环节和关键步骤。为了弄清近年来于桥水库入库河流氮、磷输入负荷,选取GWLF模型对水平口子流域的水文过程进行模拟,首先利用2006—2018年气象、水文资料率定模型水文参数,然后将参数推广到整个流域,对2019—2020年3条主要入库河流流量进行模拟,最后乘以相应河流断面的总氮、总磷浓度估算氮磷输入负荷。结果显示:GWLF模型适用于研究区的水文过程模拟,校准期和验证期的纳氏系数分别为0.89和0.91,平均相对误差分别为12.2%和13.1%;2020年总氮入库负荷为3 977.0 t,其中引滦调水贡献占57.0%,3条入库河流共贡献43.0%;总磷入库负荷为48.8 t,其中引滦调水贡献占68.6%,3条入库河流共贡献31.4%。GWLF模型输入数据需求量较少,模型参数较少,模拟效果较好,适用于中小型流域的水资源和水环境管理,具有一定的推广应用前景。     

Estimation of riverine loads of nitrogen and phosphorus to the Baltic Sea, 1970–1993

This article presents the results of the first critical examination of time series of riverine nutrient-load data for the entire Baltic Sea drainage area. Water quality data collected by or for the different national environmental agencies were compiled and analysed statistically to identify and remove inconsistent or obviously incorrect observations. Moreover, sampling tours were undertaken to acquire additional information about the present nutrient concentrations in the largest rivers in the study area. Gaps in the time series of approved data were then filled in by employing statistical interpolation and extrapolation methods. Thereafter, the concentration and runoff data were combined to obtain estimates of monthly nutrient loads for the time period 1970–93. The results of the calculations showed that although there had been substantial changes in land use, atmospheric deposition and wastewater treatment in many parts of the study area, the total riverine loads of nitrogen (N) and phosphorus (P) to the Baltic Sea have been fairly constant since 1980, and most likely also since 1970. Moreover, the interannual variation was clearly correlated to the runoff. The mean annual loads for the time period 1980–93 were found to be about 825 000 tonnes N and 41 000 tonnes P, respectively. This implies that (i) several other investigators have strongly underestimated the riverine loads of nutrients, especially the nitrogen, and that (ii) the riverine loads by far exceed the input to the Baltic Sea from other sources, {i.e.} atmospheric deposition, direct emissions from cities and industries along the Baltic Sea coast and nitrogen fixation by marine algae.     

土壤氨氮、亚硝酸盐氮、硝酸盐氮的测定试料保存实验

对测定土壤中氨氮、亚硝酸盐氲、硝酸盐氲的试料保存条件和时间进行研究。结果表明,在4℃、避光保存的条件下,试料可以保存7d,而各组份浓度值基本保持不变。其中,氨氮的本底试料值相对标准偏差为2．86％,加标试料值相对标准偏差为2．88％,加标回收率为85．8％～101％;亚硝酸盐氮加标量为0．5μg试料值相对标准偏差为3．55％,加标量为4．0μg试料值相对标准偏差为2．93％;硝酸盐氮与亚硝酸盐氮总量的本底试料值相对标准偏差为7．02％,加标试料值相对标准偏差为4．56％,加标回收率为82．6％～104％。     

2020—2022年全国入海河流总氮浓度时空特征

根据全国230个入海河流断面2020—2022年总氮质量浓度监测数据,基于时间序列统计方法和空间聚类方法,分析了总氮浓度的时空分布特征。结果显示:2020—2022年全国入海河流总氮年均质量浓度逐年上升,从(3.24±2.20)mg/L上升到(3.92±3.30)mg/L;年内总氮浓度呈现冬高夏低、春秋居中的V形季节变化规律。空间聚类分析表明:总氮质量浓度从北到南可分为4个有较明显差异的区域,分别为北方高值区(包括辽东丘陵西部、辽西丘陵、山东丘陵),北方次高值区(包括环渤海京津冀地区、苏北平原),华东区(包括长江中下游平原区、上海市、浙江省、福建省),华南区(包括广东省、广西壮族自治区、海南省)。总氮年均质量浓度分布为北方高值区>北方次高值区>华东区>华南区。北方高值区的过高总氮浓度对全国总氮浓度均值提供了超比例的贡献。同时,北方高值区和北方次高值区贡献了2020—2023年全国总氮浓度92%的增幅。此外,从空间分布上看,越往北,总氮浓度的V形季节变化规律越明显。     

在线自动监测仪与实验室国标方法测定地表水中总氮的比对分析

随着监测技术的发展,地表水中越来越多的污染物可采用自动监测仪器实现实时监测。采用自动监测与实验室国标方法测定地表水中总氮的结果是否可比以及造成差异的原因,文章根据实际样品比对实验对此进行了探讨。     

流动注射分析仪在测定水体总氮中的实验研究

总氮是衡量水质富营养化的重要指标。用传统方法分析需经过高压消解,温度和时间难以控制,且手工操作复杂、费时,误差大,影响监测结果。本文用流动注射法,以QuickChem 8000流动注射仪为平台,通过大量的精密性、准确性和实样比对实验来研究其在水质总氮测定中的应用,再用数理统计的方法（F检验、t检验）从理论上验证该方法的可行性。     

乌鲁木齐市柴窝堡湖水质变化趋势与原因分析

通过对乌鲁木齐市柴窝堡湖水质现状及11年水质变化趋势的分析,预测了柴窝堡湖"十二五"水质变化情况。通过综合分析,找出污染成因,并提出对策建议,为区域水环境保护和水体污染防治提供科学依据。     

浅谈总氮测定过程中的质量控制

着重针对水质中总氮测定时分析仪器、分析试剂和实验环境等因素对监测结果的影响,提出保证总氮监测质量的建议和措施。     

Systematic Biases in Measurement of Urban Nitrogen Dioxide using Passive Diffusion Samplers

Measurement of nitrogen dioxide using passivediffusion tube over 22 months in Cambridge, U.K. areanalysed as a function of sampler exposure time, andcompared with NO₂ concentrations obtained from aco-located chemiluminescence analyser. The averageratios of passive sampler to analyser NO₂ at acity centre site (mean NO₂ concentration 22 ppb)are 1.27 (n = 22), 1.16 (n = 34) and 1.11 (n = 7) forexposures of 1, 2 and 4-weeks, respectively. Modellingthe generation of extra NO₂ arising from chemicalreaction between co-diffusing NO and O₃ in thetube gave a ratio (modelled/measured) of 1.31 for1-week exposures. Such overestimation is greatest whenNO₂ constitutes, on average, about half of totalNO_x (= NO + NO₂) at the monitoring locality.Although 4-week exposures gave concentrations whichwere not significantly different from analyserNO₂, there was no correlation between thedatasets. At both the city-centre site and anothersemi-rural site (mean NO₂ concentration 11 ppb)the average of the aggregate of four consecutive1-week sampler exposures or of two consecutive 2-weeksampler exposures was systematically greater than fora single 4-week exposure.The results indicate two independent and opposingsystematic biases in measurement of NO₂ bypassive diffusion sampler: an exposure-timeindependent chemical overestimation with magnitudedetermined by local relative concentrations of NO andO₃ to NO₂, and an exposure-time dependentreduction in sampling efficiency. The impact of theseand other potential sources of systematic bias on theapplication of passive diffusion tubes for assessingambient concentrations of NO₂ in short (1-week)or long (4-week) exposures are discussed in detail.     

赣江主要河流丰水期-枯水期氮磷营养盐分布特征

对2006—2019年赣江水体及水库丰水期-枯水期的总氮(TN)、氨氮(NH₃-N)、硝态氮(NO^-₃-N)和总磷(TP)浓度变化和分布特征进行分析。将赣江按河谷地形和河道特征划分为上游、中游、下游3段;根据水流来源将赣江划分为章水、桃江、湘水、贡水、泸江、赣江干流。结果显示：桃江TN质量浓度在2011年枯水期取得最大值8.26 mg/L;章水TP质量浓度在2007年枯水期取得最大值0.18 mg/L,整个赣江丰水期-枯水期的TP质量浓度在0.02～0.18 mg/L范围内浮动,变化幅度较小;章水NH₃-N浓度在2008年枯水期取得最大值1.86 mg/L,而在2017—2019年NH₃-N的浓度基本处于0.5 mg/L以内,达到《地表水环境质量标准》(GB 3838—2002)Ⅲ类水质标准。万安水库和峡江水库对总氮的滞留率,丰水期分别为24.26%、17.44%,枯水期分别为21.36%、16.60%;对总磷的滞留率,丰水期分别为24.78%、19.05%,枯水期分别为33....     

大连市中心城区地下水“三氮”污染分析

依据《地下水质量标准》(GB/T 14848-1993),对大连市中心城区2006-2010年地下水"三氮"监测资料进行分析。结果表明,"三氮"的检出率(最高为100%)和超标率(最高为58.8%)都较高,其中亚硝酸盐氮超标显著。氨氮浓度各年均值均超标,呈波动变化;亚硝酸盐氮浓度各年均值均超标,并呈上升趋势;硝酸盐氮各年均值波动变化,总体呈上升趋势。除2009年以外,其他4年中丰水期的硝酸盐氮浓度都比枯水期高;除2007年外,其他4年中的丰水期氨氮浓度都比枯水期低。"三氮"最高浓度值主要出现在中心城区周边区域。     

Monitoring Nitrogen Dioxide and its Effects on Asthmatic Patients: Two Different Strategies Compared

Objectives: To develop a `methodologyassessment' to evaluate the strengths and theweaknesses of two different epidemiological approachesand to identify the best suited monitoring strategy tomeasure the effects of `normal levels' of nitrogendioxide exposure on the health of an urban population.Methodology: all exposures to nitrogen dioxidewere determined with passive samplers, each samplerconsisting of 3 measuring Palmes tubes. In the firststudy the nitrogen dioxide exposure was assessed in 23school children (11 asthmatic and 12 non asthmatic).Children wore samplers for a week and parallelmeasurements were made in their kitchens, in bedroomsand outside their homes. The second study consisted ina case-control study where the relative risk ofhospital admission was calculated considering nitrogendioxide levels in a city of northern Italy. 110asthmatic patients were compared to a control group of 5322 people.Results: Personal sampler measurementshighlighted significant differences in exposure when nitrogen dioxide atmospheric levels were compared inasthmatic and healthy children (p<0.05). No otherparameters were significant in the two groups. Asignificant action of atmospheric nitrogen dioxide onhospital admission was demonstrated (p<0.01).Conclusions: Although a cause-effect relation assuch cannot be identified, the studies show a relationbetween the exposure to nitrogen dioxide and thepresence of adverse effects on people's health.However the `disadvantage' is for subjects withasthmatic pathologies, compared to the others. Tomanage this problem most effectively, a combinedapproach with the activation of specific personalmonitoring campaigns of the subjects with verifiedrisk seems necessary. This requires `reading' the dataresulting from most extensive and up to dateinformation systems, capable of a thorough controlboth of the living environment and of the clinicaloutcome of the whole population.     

水杨酸-次氯酸盐光度法测量氨氮时pH对氨氮在线监测仪测量结果的影响

采用水杨酸-次氯酸盐光度法,研究了pH对KS2301氨氮在线监测仪测量结果的影响。研究结果表明,酸碱度对仪器测量结果的准确性均有影响,其中,酸度的影响较碱度的影响要大。当PH为11.6~11.7时,显色剂的显色效果最好,仪器在这个值附近测量结果最稳定。     

燃烧氧化-电化学法测定地表水和废水中的总氮

系统研究了燃烧氧化-电化学法测定地表水和废水中总氮的分析方法,优化了分析条件。结果表明,氧化温度700℃、反应时间6 min为优化的分析条件。该方法校正曲线线性良好(r=0.999 9),检出限最低可达0.016 mg/L。标准样品分析结果准确度高,相对误差为0.9%~7.1%。实际样品分析结果精密度为0.7%~3.4%,加标回收率为88%~117%。     

北京市河流氨氮浓度时空演变特征分析

选取2010—2017年北京市地表水监测数据,对河流氨氮(NH 3-N)浓度的时空演变特征进行分析。结果显示,空间上,全市河流NH 3-N浓度整体上保持上游优于下游的分布特征;年均浓度显著下降,由2010年的8.53 mg/L逐年下降至2017年的3.09 mg/L;河流NH 3-N浓度与化学需氧量、总磷呈显著正相关,与溶解氧显著负相关,总氮与NH 3-N的比值随着水质由差到好呈上升状态。污水收集处理和再生水利用是改善北京市河流水质的关键措施。为持续降低河流NH 3-N浓度,改善首都水环境质量,须提高污水处理能力和出水水质,有机结合再生水回用与生态治水理念。     

连续流动分析法测定地表水中总氮

采用50 mm流动检测池,建立了连续流动分析法测定地表水中总氮。方法检出限为0.02 mg/L,水样加标回收率为100%~101%,平行样品相对偏差为0.10%~0.27%,精密度(RSD,n=6)为0.72%~1.10%。实验结果表明,该方法准确可靠、灵敏度高、重现性好、分析速度快、操作简便,适用于地表水中总氮的分析。     

水污染源氨氮自动监测设备比对试验考核指标探讨

对15家氨氮自动监测设备比对试验考核不合格的污水厂及印染厂的考核情况进行了分析，发现目前水污染源氨氮自动监测设备比对试验考核指标存在一些问题。结合水污染源在线监测系统运行与考核技术规范以及地表水自动监测技术规范，提出了水污染源氨氮自动监测系统按照不同排放浓度实施不同比对试验考核指标的建议。     

水和废水中亚硝酸盐氮的现场快速分析方法研究

在现行水中亚硝酸盐氮分析方法的基础上,通过试验研究,采用便携式分光光度计建立了水体中亚硝酸盐氮的分析方法。该法与GB7493-87[N-(1-萘基)-乙二胺光度法]具有良好的可比性,分析结果的精密度和准确度均为良好,该方法可在现场简便快速测定水和废水中的亚硝酸盐氮。     

CFA1000连续流动分析系统测定水中总氮

通过绘制总氮的校准曲线,测定仪器的空白值、检出限和测定下限,并对仪器的A类不确定度进行评价,对比CFA1000连续流动分析系统与SKALAR SAN++型流动分析仪测定方法、国标法测定方法的分析结果。结果表明,在保证测定结果准确度和精密度的前提下,CFA1000连续流动分析系统具有较好的测试灵敏度。     

Temporal and Spatial Variation of Nutrient Levels in the Nemunas River (Lithuania and Belarus)

There are discordant results on trends in nutrient river water quality from the economical transition countries in Europe. The present study assessed the impact of these economical changes on the load and concentration at 17 monitoring stations along the Nemunas River and its major tributaries (Lithuania and Belarus). Three time periods were evaluated: the Soviet rule command system period 1986–1991, the transfer to market economy period 1992–1996 and the post reform period 1997–2002. The most surprising result in this study, was the increased area-specific load of NO₃-N from the first to the third period at almost all the sampling sites. The increase was particularly large (43–78%) at the sites in the Lithuanian part of the river. The corresponding load increase in the Belarussian part of the river was only 1–15%. The statistical analyses of concentration data confirm the strong upward NO₃-N trend at the Nemunas mouth and at 5 of the 6 tributaries in the lower part of Nemunas. Temporal and spatial analysis of nitrates transport in the Nemunas River and its main tributaries revealed that nitrates mainly originate from agricultural areas. The upward trends were most likely an effect of ploughing of pastures and unbalanced crop fertilisation in combination with large storage and accumulation of soil-nitrogen during the Soviet period.On contrary to nitrate-N, the area-specific load of PO₄-P decreased significantly from the first to the third period at all sites along the Nemunas River (31–86%). Seasonal (SMK) and Partial (PMK) Mann-Kendall tests on PO₄-P concentrations also showed significant downward trend at 14 of 16 investigated sites. The decrease of PO₄-P levels was attributed to the reduction of municipal and industrial point source emissions and to the decreased livestock numbers.The NH₄-N load showed the same pattern as PO₄-P. At the river mouth the load was 90 kg km⁻² yr⁻¹ during the first period compared to only 20–30 kg km⁻² yr⁻¹ in the third period. The trend test on NH₄-N concentrations detected significant downward trends at 5 out of 16 sites. The declines were explained by decreased emissions from cities and large animal breeding farms.This study showed that trend analysis at multiple sites in a river basin is crucial for the understanding of the variability in time and space. Such analysis is also important for our interpretation of underlying sources and fluxes in a drainage basin over time. This is particularly important for compounds that have different source origin.