湿法氧化法分析水中有机~(14)C的初步实验研究

碳元素是生物体有机物的基本组成成分,很容易被活机体吸收同化。而~(14)C是低能纯β辐射体,具有很长的半衰期(5730年)和很高的同位素交换率,会对生物体产生内照射剂量,而水是地球大气圈、水圈、生物圈和岩石圈联系的纽带,因此水中~(14)C的测量方法受到人们的广泛关注。有机~(14)C作为水中~(14)C的一个重要组成部分,测量方法显得尤为重要。水中~(14)C采用过硫酸钾-硝酸银的湿法氧化法作前处理,碳酸钙粉末悬浮法制样,液闪谱仪测量,开展了初步的实验研究。方法回收率为96.4%,探测下限为0.40Bq/L(样品量60mL,测量时间300min),加标样品的实验结果表明该方法可应用于水样品中~(14)C的分析测量。     

水质改性工艺原理和现场管理探讨

中原油田的注入水是一种由CO2-HCO-3构成的弱酸性缓冲体系,具有很强的腐蚀倾向,增加了水处理的难度。通过加入一种以OH-为主要成份的调整剂,对水中离子进行重新调整,除掉水中的CO2和HCO-3离子,使水中离子形成热力学或动力学的稳定分布,从而抑制使水质变劣的化学反应,使水质沿注水流程达标。通过几年的实践,表明该工艺在处理油田污水方面具有可行性和实效性。采用该工艺的污水处理站水质全面达标。     

低本底α/β测量仪测定水中锶-90质量控制实践与分析

对低本底α/β测量仪测定水中锶-90质量控制进行实践与分析,通过对仪器本底与监督源效率短期、长期稳定性,检测过程空白、精密度、准确度进行分析,采取泊松分布检验、质量控制图、效率重复性、空白显著性检验、相对偏差和回收率为控制方式,探讨了本实验室测定水中锶-90质量控制结果。根据结果表明本实验室4个通道本底满足泊松分布检验,本底和监督源长期稳定性监测结果均在质控图的UCL (上控制线)与LCL (下控制线)范围内,4个通道对监督源的探测效率、重复性均满足JJG 853-2013方法要求,样品空白结果与仪器本底无显著性差异,样品精密度测量结果满足HJ815-2016方法中要求,加标回收率满足HJ 61-2021方法中要求。通过本文采取的质量控制实践,能够为指导低本底α/β测量仪准确测定水中锶-90提供实践案例,同时为今后改进此类低水平水中锶-90的测量精度提供借鉴意义。     

环境中的氚及其监测

本文概述氚的性质、来源及其对环境的污染和危害。介绍了水的电解浓缩—液体闪烁计数法探测水中氚的实验程序。     

膨润土/过硫酸盐协同处理罗丹明B废水的研究

实验研究了膨润土和过硫酸盐协同去除水中的罗丹明B(RhB)。比较了4种不同体系中RhB的去除效率,并考察了不同因素对RhB去除效率的影响。结果表明,在单纯的PS和PMS体系中,RhB的去除率仅为22.97%和25.63%。而在Bt/PS和Bt/PMS体系中,去除率高达86.66%和98.32%,可见膨润土与过硫酸盐明显存在协同作用,且膨润土对PMS的协同作用强于PS。当过硫酸盐与RhB的摩尔比为5∶1,pH为3,反应温度为30℃时,Bt/PS和Bt/PMS体系能在30min内完全去除水中的RhB。     

γ能谱分析环境质量气溶胶核素活度浓度探测下限敏感性分析

根据敏感性分析原理,导出探测下限敏感性分析公式,分析探测下限与探测效率、采样体积、谱仪系统本底以及测量时间的敏感性,表明采样体积敏感性最高、谱仪本底敏感性次之、探测效率和测量时间敏感性相同且最低。实际工作中可以采用压制样品减小样品高度方式来有效降低探测下限。     

液相色谱—电感耦合等离子体质谱联用测定水质有机锡化合物的前处理方法研究

采用液液萃取前处理方法对水中的有机锡进行提取,并在一定的分析条件下用液相色谱—电感耦合等离子体质谱联用（HPLC-ICP-MS）分析法,测定水中的二苯基锡、二丁基锡、三苯基锡和三丁基锡4种有机锡化合物。为了提高前处理的萃取效率,研究了萃取溶剂、萃取次数和萃取酸度不同时对萃取效率的影响。     

炸药爆轰气体产物中无机组份的离子色谱分析方法研究

采用超纯水、Na2CO3-NaHCO3NaOH3种不同的吸收液吸收爆轰气体产物、离子色谱进行样品分离、外标法定量,建立了爆轰气体产物中HF、HCl、HCN无机污染物的离子色谱分析方法。研究表明,炸药爆轰气体中合有一定量的HF、HCl和少量的HCN,选择3．2mmol／LNa2C03与1．0mmol／LNaHCO3混合溶液作为爆轰产物中无机组份的吸收液,吸收效率均值太于90％;离子色谱分析方法的相对标准偏差（RSD）小于5．0％,相关系数达到0．9990以上;进样量为100μL时,HF、HCl、HCN的检测限分别为0．04mg／m^3、0．03mg／m^3、0．05mg／m^3。该方法灵敏度高,回收率好,且样品预处理简单。     

高含CO2天然气运输管道缓蚀剂的筛选

大多数天然气藏CO2含量为10%~98%,CO2在不同的温度、压力条件下腐蚀极其严重。文章主要针对高含CO2天然气运输管道腐蚀的问题,开展缓蚀剂的筛选,重点开展CO2腐蚀规律研究与实验,评价环境温度、CO2分压、流动速度对腐蚀规律的影响,明确缓蚀剂的影响因素,结合管材的材质,优选评价不同类型的缓蚀剂,缓蚀效率分别为90.53%和92.64%,在管道凝液介质的气相及液相中都有较高的缓蚀效率。通过设计现场加药工艺及制度,监测评价缓蚀剂缓释效果和腐蚀情况,可防止管道运输过程中CO2腐蚀的侵害,长输管线内腐蚀控制良好。     

嘉陵江C市段源水中有机污染物定性研究

采用XAD-2树脂富集水中有机物，用GC＼MS进行定性分析。对嘉陵江C市段水源水中有机污染物进行分析，共检出有机污染物13种，其中以多环芳烃，邻苯二甲酸酯类为主，并且有3种物质为中国环境优先控制污染物，分别是邻苯二甲酸二辛酯，邻苯二甲酸二丁酯、荧蒽。     

INFLUENCE OF DIFFERENT TEMPORAL SAMPLING STRATEGIES ON ESTIMATING TOTAL PHOSPHORUS AND SUSPENDED SEDIMENT CONCENTRATION AND TRANSPORT IN SMALL STREAMS1

ABSTRACT: Various temporal sampling strategies are used to monitor water quality in small streams. To determine how various strategies influence the estimated water quality, frequently collected water quality data from eight small streams (14 to 110 km²) in Wisconsin were systematically subsampled to simulate typically used strategies. These subsets of data were then used to estimate mean, median, and maximum concentrations, and with continuous daily flows used to estimate annual loads (using the regression method) and volumetrically weighted mean concentrations. For each strategy, accuracy and precision in each summary statistic were evaluated by comparison with concentrations and loads of total phosphorus and suspended sediment estimated from all available data. The most effective sampling strategy depends on the statistic of interest and study duration. For mean and median concentrations, the most frequent fixed period sampling economically feasible is best. For maximum concentrations, any strategy with samples at or prior to peak flow is best. The best sampling strategy to estimate loads depends on the study duration. For one‐year studies, fixed period monthly sampling supplemented with storm chasing was best, even though loads were overestimated by 25 to 50 percent. For two to three‐year load studies and estimating volumetrically weighted mean concentrations, fixed period semimonthly sampling was best.     

Nutrient and sediment removal by a restored wetland receiving agricultural runoff

Few studies have measured removal of pollutants by restored wetlands that receive highly variable inflows. We used automated flow-proportional sampling to monitor the removal of nutrients and suspended solids by a 1.3-ha restored wetland receiving unregulated inflows from a 14-ha agricultural watershed in Maryland, USA. Water entered the wetland mainly in brief pulses of runoff, which sometimes exceeded the 2500-m3 water holding capacity of the wetland. Half of the total water inflow occurred in only 24 days scattered throughout the two-year study. Measured annual water gains were within 5% of balancing water losses. Annual removal of nutrients differed greatly between the two years of the study. The most removal occurred in the first year, which included a three-month period of decreasing water level in the wetland. In that year, the wetland removed 59% of the total P, 38% of the total N, and 41% of the total organic C it received. However, in the second year, which lacked a drying period, there was no significant (p > 0.05) net removal of total N or P, although 30% of the total organic C input was removed. For the entire two-year period, the wetland removed 25% of the ammonium, 52% of the nitrate, and 34% of the organic C it received, but there was no significant net removal of total suspended solids (TSS) or other forms of N and P. Although the variability of inflow may have decreased the capacity of the wetland to remove materials, the wetland still reduced nonpoint-source pollution.     

Precipitation and river water chemistry of the Piracicaba River basin, southeast Brazil

Annual precipitation and river water volumes and chemistry were measured from 1995 to 1998 in a mesoscale agricultural area of southeast Brazil. Precipitation was mildly acidic and solute concentrations were higher in the west than in the east of the basin. Combustion products from biomass burning, automobile exhaust, and industry typically accumulate in the atmosphere from March until October and are responsible for seasonal differences observed in precipitation chemistry. In river waters, the volume-weighted mean (VWM) concentrations of major solutes at 10 sites across the basin were generally lower at upriver than at downriver sampling sites for most solutes. Mass balances for major solutes indicate that, as a regional entity, the Piracicaba River basin was a net sink of H+, PO4(3-), and NH4+, and a net source of other solutes. The main stem of the Piracicaba River had a general increase in solute concentrations from upriver to downriver sampling sites. In contrast, NO3- and NH4+ concentrations increased in the mid-reach sampling sites and decreased due to immobilization or utilization in the mid-reach reservoir, and there was denitrification immediately downriver of this reservoir. Compared with tributaries of the Chesapeake Bay estuary, the Piracicaba River is affected more by point-source inputs of raw sewage and industrial wastes than nonpoint agricultural runoff high in N and P. Inputs of N and C are responsible for a degradation of water quality at downriver sampling sites of the Piracicaba River drainage, and water quality could be considerably improved by augmenting sewage treatment.     

AUTOMATIC BOTTLE SEALING MECHANISM FOR SEQUENTIAL SAMPLING OF VOLATILE ORGANICS IN WATER1

ABSTRACT: The design, construction, and evaluation of two automatic bottle sealing mechanisms for the collection of volatile organic compounds in water are described. Manually collected samples were either stored in uncapped bottles or in bottles capped with the automatic bottle sealing mechanisms. After 24 hours' storage, significant losses of volatile compounds from uncapped samples occurred even if the samples were stored at 4°C, but not for the samples capped with the automatic bottle sealing mechanisms. The mechanism for sealing the sample bottles was integrated into a commercial sampler with minor modifications to the sampler. The sampling system was then evaluated under controlled conditions to simulate actual field sampling. The results showed that the system was suitable for taking sequential discrete water samples automatically for 24 hours without significant losses of volatile organic compounds.     

Summary of well water sampling in California to detect pesticide residues resulting from nonpoint-source applications

This report summarizes well sampling protocols, data collection procedures, and analytical results for the presence of pesticides in ground water developed by the California Department of Pesticide Regulation (DPR). Specific well sampling protocols were developed to meet regulatory mandates of the Pesticide Contamination Prevention Act (PCPA) of 1986 and to provide further understanding of the agronomic, chemical, and geographic factors that contribute to movement of residues to ground water. The well sampling data have formed the basis for the DPR's regulatory decisions. For example, a sampling protocol, the Four-Section Survey, was developed to determine if reported detections were caused by nonpoint-source agricultural applications, a determination that can initiate formal review and subsequent regulation of a pesticide. Selection of sampling sites, which are primarily rural domestic wells, was initially based on pesticide use and cropping patterns. Recently, soil and depth-to-ground water data have been added to identify areas where a higher frequency of detection is expected. In accordance with the PCPA, the DPR maintains a database for all pesticide well sampling in California with submission required by all state agencies and with invitations for submission extended to all local and federal agencies or other entities. To date, residues for 16 active ingredients and breakdown products have been detected in California ground water as a result of legal agricultural use. Regulations have been adopted for all detected parent active ingredients, and they have been developed regardless of the level of detection.     

Potential mineralization of four herbicides in a ground water--fed wetland area

Herbicides may leach from agricultural fields into ground water feeding adjacent wetlands. However, only little is known of the fate of herbicides in wetland areas. The purpose of the study was to examine the potential of a riparian fen to mineralize herbides that could leach from an adjacent catchment area. Slurries were prepared from sediment and ground water collected from different parts of a wetland representing different redox conditions. The slurries were amended with O2, NO3-, SO4(2-), and CO2, or CO2 alone as electron acceptors to simulate the in situ conditions and their ability to mineralize the herbides mecoprop, metsulfuron-methyl, isoproturon and atrazine. In addition, the abundance of bacteria able to utilize O2, NO3-, SO4(2-) + CO2, and CO2 as electron acceptors was investigated along with the O2-reducing and methanogenic potential of the sediment. The recalcitrance to bacterial degradation depended on both the type of herbicide and the redox conditions pertaining. Mecoprop was the most readily degraded herbicide, with 36% of [ring-U-14C]mecoprop being mineralized to 14CO2 under aerobic conditions after 473 d. In comparison, approximately 29% of [phenyl-U-14C]metsulfuron-methyl and 16% of [ring-U-14C]isoproturon mineralized in aerobic slurries during the same period. Surprisingly, 8 to 13% of mecoprop also mineralized under anaerobic conditions. Neither metsulfuron-methyl nor isoproturon were mineralized under anaerobic conditions and atrazine was not mineralized under any of the redox conditions examined. The present study is the first to report mineralization of meco-prop in ground water in a wetland area, and the first to report mineralization of a phenoxyalcanoic acid herbicide under both aerobic and anaerobic conditions.     

Evaluating the effects of spatial monitoring policy on groundwater quality portrayal

What size sample is sufficient for spatially sampling ambient groundwater quality? Water quality data are only as spatially accurate as the geographic sampling strategies used to collect them. This research used sequential sampling and regression analysis to evaluate groundwater quality spatial sampling policy changes proposed by California's Department of Water Resources. Iterative or sequential sampling of a hypothetical groundwater basin's water quality produced data sets from sample sizes ranging from 2.8% to 95% coverage of available point sample sites. Contour maps based on these sample data sets were compared to an original (control), mapped hypothetical data set, to determine at which point map information content and pattern portrayal are not improved by increasing sample sizes. Comparing series of contour maps of ground water quality concentration is a common means of evaluating the geographic extent of groundwater quality change. Comparisons included visual inspection of contout maps and statistical tests on digital versions of these map files, including correlation and regression products. This research demonstrated that, down to about 15% sample site coverage, there is no difference between contour maps produced from the different sampling strategies and the contout map of the original data set.     

MONITORING STRATEGIES TO DETERMINE COMPLIANCE WITH WATER QUALITY OBJIECTIVES1

ABSTRACT: Two sampling strategies designed to test for compliance with water quality objectives are examined. For objectives based on long-term mean requirements, fixed frequency sampling at frequent intervals is most advantageous regardless of the underlying distribution of the data. For objectives that are based on maximum allowable concentrations, effective sampling strategies increase the likelihood of detecting noncompliance. If data are highly autocorrelated or sharply seasonal in distribution, an exceedance-driven sampling strategy is more effective and efficient for detecting violations than fixed frequency sampling. However, data generated by exceedance-driven sampling provide biased estimates of mean and standard deviation.     

QUANTITATIVE METHODS FOR PRELIMINARY DESIGN OF WATER QUALITY SURVEILLANCE SYSTEMS1

ABSTRACT: To assure attainment and maintenance of desired water quality levels in our rivers and streams, systematic monitoring must be performed. A preliminary phase of the design of water quality surveillance systems is the specification of sampling frequencies and station locations throughout the basin; that is, the development of an adequate space/time sampling plan. The purpose of this paper is to present some quantitative methods which have been developed to identify candidate sets of sampling frequencies and station locations, and to establish priorities for implementing the different frequencies and locations. These methods are useful in the cost/effectiveness trade-off analyses in surveillance system design, and are based on the surveillance system objective of pollution abatement in which it is desired to detect violations in state-federal water quality standards. A spatial priority measure is developed which is dependent both on the water quality profile in the stream and on the information obtained from monitoring stations located in other reaches. Also, a temporal sampling priority rating is presented which is a measure of the effectiveness of the surveillance system with respect to its ability to detect the violations in the standards. To illustrate the quantitative methods, the procedures are applied to the Wabash River Basin.     

RESERVOIR WATER QUALITY SAMPLING DESIGN1

ABSTRACT: The design of monitoring programs often serves as one of the major sources of error or uncertainty in water quality data. Properly designed programs should minimize uncertainty or at least provide a means by which variability can be partitioned into recognizable components. While the design of sampling programs has received recent attention, commonly employed strategies for limnological sampling of lakes may not be completely appropriate for many reservoirs. Based on NES data, reservoirs are generally larger, deeper, and morphologically more complex than natural lakes. Reservoirs also receive a majority of their inflow from a single tributary located a considerable distance from the point of outflow. The result is the establishment of marked physical, biological, and chemical gradients from headwater to dam. The existence of horizontal as well as vertical gradients, and their importance in water quality sampling design were the subject of intensive transect sampling efforts at DeGray Lake, a U.S. Army Corps of Engineers reservoir in southern Arkansas. Data collected were used to partition Variance, identify areas of similarity, and demonstrate how an equitable sampling program might be designed.