Performance of semipermeable membrane devices for sampling of organic contaminants in groundwater

Lipid-filled semipermeable membrane devices (SPMDs) are receiving increasing attention as passive, in situ samplers for the assessment of environmental pollutant exposure. Although SPMDs have been successfully used in a variety of field studies in surface waters, only a few studies have addressed their characteristics as groundwater samplers. In this study, the performance of the SPMDs for monitoring organic contaminants in groundwater was evaluated in a pilot field application in an area severely contaminated by chemical waste, especially by chlorinated hydrocarbons. The spatial distribution of hydrophobic groundwater contaminants was assessed using a combination of passive sampling with SPMDs and non-target semiquantitative GC-MS analysis. More than 100 contaminants were identified and semiquantitatively determined in SPMD samples. Along the 6 field sites under investigation, a large concentration gradient was observed, which confirms a very limited mobility of hydrophobic substances in dissolved form in the aquifer. The in situ extraction potential of the SPMD is limited by groundwater flow, when the exchange volume of well water during an exposure is lower than the SPMD clearance volume for the analytes. This study demonstrates that SPMDs present a useful tool for sampling and analyzing of groundwater polluted with complex mixtures of hydrophobic chemicals and provides guidance for further development of passive sampling technology for groundwater.     

Trophic dynamics of U, Ni, Hg and other contaminants of potential concern on the Department of Energy’s Savannah River Site

The Department of Energy’s Savannah River Site is a former nuclear weapon material production and current research facility located in South Carolina, USA. Wastewater discharges from a fuel and nuclear reactor target manufacturing facility released depleted and natural U, as well as other metals into the Tims Branch-Steed Pond water system. We investigated the current dynamics of this system for the purposes of environmental monitoring and assessment by examining metal concentrations, bioavailability, and trophic transfer of contaminants in seven ponds. Biofilm, detritus, and Anuran and Anisopteran larvae were collected and analyzed for stable isotopes (δ ¹⁵N, δ ¹³C) and contaminants of potential concern (COPC) with a focus on Ni, U, and Hg, to examine metal mobility. Highest levels of Ni and U were found in biofilms U (147 and 332 mg kg^?1 DW, respectively), while highest Hg levels were found in tadpoles (1.1 mg kg^?1 DW). We found intraspecific biomagnification of COPCs as expressed through stable isotope analysis. Biofilms were the best indicators for contamination and Anuran larvae with the digestive tract removed were the best indicators of the specific bioavailability of the focal metals. Monitoring data showed that baseline δ ¹⁵N values differed between ponds, but within a pond, values were stable throughout tadpole Gosner stage, strengthening the case to use this species for monitoring purposes. It is likely that there still is risk to ecosystem integrity as COPC metals are being assimilated into lower trophic organisms and even low levels of this mixture has shown to produce deleterious effects to some wildlife species.     

Economics of place-based monitoring under the safe drinking water act, part I: spatial and temporal patterns of contaminants, and design of screening strategies

The goals of environmental legislation and associated regulations are to protect public health, natural resources, and ecosystems. In this context, monitoring programs should provide timely and relevant information so that the regulatory community can implement legislation in a cost-effective and efficient manner. The Safe Drinking Water Act (SDWA) of 1974 attempts to ensure that public water systems (PWSs) supply safe water to its consumers. As is the case with many other federal environmental statutes, SDWA monitoring has been implemented in relatively uniform fashion across the USA. In this three part series, spatial and temporal patterns in water quality data are utilized to develop, compare, and evaluate the economic performance of alternative place-based monitoring approaches to current monitoring practice. Under the Safe Drinking Water Act (SDWA), a common list of over 90 contaminants is analyzed nationwide using EPA-authorized laboratory procedures. National and state-level summaries of SDWA data have shown that not all contaminants occur in all places at all times. This hypothesis is confirmed and extended by showing that only a few (less than seven) contaminants are of concern in any one of 19 Iowa surface water systems studied. These systems collectively serve about 350,000 people and their sizes vary between 1,200 and 120,000. The distributions of contaminants found in these systems are positively skewed, with many non-detect measurements. A screening strategy to identify such contaminants in individual systems is presented. These findings have significant implications not only for the design of alternative monitoring programs, but also in multi-billion-dollar decisions that influence the course of future drinking water infrastructure, repair, and maintenance investments.     

Determination of total and partially extractable solid-bound element concentrations using collision/reaction cell inductively coupled plasma-mass spectrometry and their significance in environmental studies

Determination of solid-bound element concentrations is an important initial step in environmental studies especially for assessment of contamination level, and of origin, relative mobility, and fate of contaminants. This study revealed that a relatively new collision/reaction cell inductively coupled plasma-mass spectrometry is a potent tool for determining total and partially extractable solid-bound element (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, and Pb) concentrations in a complex matrix solution containing HF and/or HCl. Six different extraction methods commonly used for environmental monitoring studies were tested for their bias and variability using estuarine and marine standard reference materials. Microwave-assisted methods based on concentrated [HNO₃] or [HNO₃?+?HF (4:1)] and [HNO₃?+?HF?+?HCl (10:3:2)] were applied for determining pseudo-total and total element concentrations, respectively. Dilute-acids (1 M HNO₃, 1 M HCl, and 0.5 M HCl) were utilized in single-step partial extraction protocols. Except the 0.5 M HCl cold-extraction method which was performed at room temperature, other partial extraction protocols used microwave-digestion. This study demonstrated that the use of microwave-assisted methods in studies aimed at determining the non-residual, non-specific extractable fractions of elements in solid environmental samples may result in overestimation, and thus needs to be re-examined. We believe that the cold extraction method will play a significant role in future environmental monitoring studies. Nevertheless, results of the cold extraction method not accompanied with total element concentrations have limited value, as the amount of extraction may vary significantly with the nature (origin) of the elements, and with the types of the samples. Therefore, we suggest combining microwave-assisted total digestion and 0.5 M HCl cold-extraction methods as a relatively cost- and time-effective, environmentally sound screening procedure for routine environmental monitoring programs involving a large number of samples from diverse geological and anthropogenic settings.     

Determination of synthetic musk compounds in sewage biosolids by gas chromatography/mass spectrometry

A review of sewage sludge regulations and land application practices by the United States National Research Council (2002) recommended development of improved analytical techniques to adequately identify and quantify new chemical contaminants, such as synthetic musk compounds in Class A sewage sludge (i.e., biosolids). This prompted the development of a rugged analytical method using gas chromatography coupled to mass spectrometry to detect this group of organic pollutants in biosolids. In this paper, the term "biosolids" is used interchangeably with "sewage sludge", which is defined in the regulations and used in the statue (Clean Water Act). Samples of Class A biosolids obtained from sewage treatment plants in Los Angeles, California, the City of Las Vegas, Nevada, and also in the form of a commercial fertilizer, were extracted using pressurized liquid extraction technique, subjected to gel permeation chromatography clean-up, and analyzed by GC/MS using the selected ion monitoring mode. The method developed has the potential to detect synthetic musk compounds in complex matrices, may provide accurate data useful in human health and environmental risk assessment, and may be useful in determining the efficacy of municipal sewage treatment plants for removing synthetic musk compounds.     

基于智能手机的环境监测光学传感器研究与应用进展

传统环境污染物生物化学分析技术通常依赖于实验室设备和专业的操作技术人员,限制了此类技术在环境应急等现场分析中的应用。以手机内置光学功能模块作为信号接收器的智能手机光学传感器,通过分析光信号可实现对目标物的定性或定量分析,其开发和应用是当前环境污染物现场快速生物化学分析检测领域的研究热点。综述了比色、荧光和化学发光3种智能手机环境监测光学传感器的传感原理、实现路径、监测指标、研究现状以及所面临的挑战,探讨了其在环境监测领域的典型应用,展望了未来的发展前景,以期为智能手机光学传感技术在环境监测领域的进一步发展提供参考。     

Monitoring water quality in Sydney Harbour using blue mussels during remediation of the Sydney Tar Ponds,Nova Scotia,Canada

Using mussels as monitoring tools we measured water quality in Sydney Harbour during a large scale, multi-year remediation project of the Sydney Tar Ponds (STPs); one of Canada's most contaminated sites. Chemical contaminants were measured in blue mussels (Mytilus edulis) in Sydney Harbour, which were used as monitoring tools to assess the spatio-temporal distribution of polycyclic aromatic hydrocarbons (PAHs); polychlorinated biphenyls (PCBs); metals (As, Cd, Cu, Hg, Pb, Zn) and lipid content during baseline and 3 years of remediation. The overall spatio-temporal distribution of chemicals in mussels was also compared to contaminants in other marine indicators (e.g., sediment, water and crab tissue). Measured metal concentrations in mussels showed some minor temporal variability (4 years), but these did not appear to be directly related to remediation activities, with the highest concentrations of As, Hg and Zn measured at reference stations. Most measured contaminants showed stable or potentially decreasing concentrations during the study, except Pb and Zn. Individual PAH compounds were mostly undetected during baseline and remediation, except for fluoranthene and pyrene. Concentrations of fluoranthene in mussels and deep water samples were moderately related. Generally, PCBs were undetected (<0.05 μg g^?1), except during year 2 remediation at some near-field stations. Contaminants measured during this study were at much lower concentrations than previously reported in other studies of mussels in Sydney Harbour and eastern Canada. This is likely due to the ongoing natural recovery of Sydney Harbour and to a lesser extent because of the environmental mitigation protection measures implemented during remediation activities at the STPs. The lack of detection of most individual PAHs and PCBs, plus relatively low bio-accumulation of metals observed during baseline and remediation attest to the effectiveness of using mussels as monitoring tools for environmental quality.     

Visualising the equilibrium distribution and mobility of organic contaminants in soil using the chemical partitioning space

Assessing the behaviour of organic chemicals in soil is a complex task as it is governed by the physical chemical properties of the chemicals, the characteristics of the soil as well as the ambient conditions of the environment. The chemical partitioning space, defined by the air-water partition coefficient (K(AW)) and the soil organic carbon-water partition coefficient (K(OC)), was employed to visualize the equilibrium distribution of organic contaminants between the air-filled pores, the pore water and the solid phases of the bulk soil and the relative importance of the three transport processes removing contaminants from soil (evaporation, leaching and particle erosion). The partitioning properties of twenty neutral organic chemicals (i.e. herbicides, pharmaceuticals, polychlorinated biphenyls and volatile chemicals) were estimated using poly-parameter linear free energy relationships and superimposed onto these maps. This allows instantaneous estimation of the equilibrium phase distribution and mobility of neutral organic chemicals in soil. Although there is a link between the major phase and the dominant transport process, such that chemicals found in air-filled pore space are subject to evaporation, those in water-filled pore space undergo leaching and those in the sorbed phase are associated with particle erosion, the partitioning coefficient thresholds for distribution and mobility can often deviate by many orders of magnitude. In particular, even a small fraction of chemical in pore water or pore air allows for evaporation and leaching to dominate over solid phase transport. Multiple maps that represent soils that differ in the amount and type of soil organic matter, water saturation, temperature, depth of surface soil horizon, and mineral matters were evaluated.     

Parasites of Fish as Indicators of Environmental Stress

During the 1994/1995 EMAP-Estauries program in the Carolinian Province we investigated the feasibility of using parasites of fish as response indicators. Parasites of fish are an indigenous component of healthy ecosystems. Within the EMAP-E design, the suite of environmental parameters which may affect parasite abundance, richness, prevalence, and diversity can be divided into three categories: 1) the physical and chemical characteristics of the water and sediment (including contaminants) external to the fish; 2) the internal environment defined by the physical condition (physiological) of individual fish; and 3) the presence and relative abundance of benthic macroinvertebrates, many of which serve as intermediate hosts. The biotic response of parasites to environmental stressors is also reflected in the health of fish. Parasite assemblages of silver perch Bairdiella chrysura respond to both natural and anthropogenic stressors. Our results showed that particular environmental stressors and specific parasites that respond include: temperature and monogeneans; contaminants and nematodes; low dissolved oxygen and protists; and salinity, together with a mixture of metal and organic contaminants and crustacea. Parasites of fish are useful biomarkers and appear to be more sensitive to environmental stressors than are the fish themselves. Parasite responses to selected environmental stressors may be used to discriminate polluted and unpolluted sites. The use of parasites of fish as biomarkers has relevant application to fisheries management and coastal monitoring programs.     

Economics of place-based monitoring under the safe drinking water act, part II: Design and development of place-based monitoring strategies

The goals of environmental legislation and associated regulations are to protect public health, natural resources, and ecosystems. In this context, monitoring programs should provide timely and relevant information so that the regulatory community can implement legislation in a cost-effective and efficient manner. The Safe Drinking Water Act (SDWA) of 1974 attempts to ensure that public water systems (PWSs) supply safe water to its consumers. As is the case with many other federal environmental statutes, SDWA monitoring has been implemented in relatively uniform fashion across the United States. In this three part series, spatial and temporal patterns in water quality data are utilized to develop, compare, and evaluate the economic performance of alternative place-based monitoring approaches to current monitoring practice. Part II: Several factors affect the performance of monitoring strategies, including: measurable objectives, required precision in estimates, acceptable confidence levels of such estimates, available budget for sampling. In this paper, we develop place-based monitoring strategies based on extensive analysis of available historical water quality data (1960-1994) of 19 Iowa community water systems. These systems supply potable water to over 350,000 people. In the context of drinking water, the objective is to protect public health by utilizing monitoring resources to characterize contaminants that are detectable, and are close to exceeding health standards. A place-based monitoring strategy was developed in which contaminants were selected based on their historical occurrence, rather than their appearance on the SDWA contaminant list. In a subset of the water systems, the temporal frequency of monitoring for one ubiquitous contaminant, nitrate, was tailored to patterns in its historical occurrence and concentration. Three sampling allocation models (linear, quadratic, and cubic) based on historic patterns in peak occurrence were developed and evaluated. Random and fixed-interval sampling strategies within the context of such models were also developed and evaluated. Strategies were configured to incorporate a variety of options for frequency and number of samples (depending on budget and the desired precision in estimate of peak concentrations).     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

Empirical evaluation of spatial and non-spatial European-scale multimedia fate models: results and implications for chemical risk assessment

Multimedia environmental fate models are commonly-applied tools for assessing the fate and distribution of contaminants in the environment. Owing to the large number of chemicals in use and the paucity of monitoring data, such models are often adopted as part of decision-support systems for chemical risk assessment. The purpose of this study was to evaluate the performance of three multimedia environmental fate models (spatially- and non-spatially-explicit) at a European scale. The assessment was conducted for four polycyclic aromatic hydrocarbons (PAHs) and hexachlorobenzene (HCB) and compared predicted and median observed concentrations using monitoring data collected for air, water, sediments and soils. Model performance in the air compartment was reasonable for all models included in the evaluation exercise as predicted concentrations were typically within a factor of 3 of the median observed concentrations. Furthermore, there was good correspondence between predictions and observations in regions that had elevated median observed concentrations for both spatially-explicit models. On the other hand, all three models consistently underestimated median observed concentrations in sediment and soil by 1-3 orders of magnitude. Although regions with elevated median observed concentrations in these environmental media were broadly identified by the spatially-explicit models, the magnitude of the discrepancy between predicted and median observed concentrations is of concern in the context of chemical risk assessment. These results were discussed in terms of factors influencing model performance such as the steady-state assumption, inaccuracies in emission estimates and the representativeness of monitoring data.     

The Effects of Application of Poultry Manure to Crude Oil Polluted Soils on Maize (Zea Mays) Growth and Soil Properties

A Figaro-type gas sensor system was investigated for the monitoring of volatile organic contaminants (VOC) in the exhaust gas from a soil vapor extraction (SVE) process. Benzene, toluene, ethyl benzene and xylene (BTEX), and their mixtures, were tested as representative contaminants. Reasonably good correlation factors >0.98 were obtained between the GC analyses and the sensor responses for each component, and for the total gas concentrations. Although the composition of the exhaust gas from SVE process, as well as the amount of each component, change with time, the sensor can be used to estimate the residual amount of contaminants by measuring the total concentrations in the exhaust gas. The sensor can be utilized as a valuable tool for the monitoring of SVE process by indicating when the operation to remediate a contaminated site should be stopped. The proposed ceramic gas sensor system may be a good alternative to existing methods, because it can satisfy the essential monitoring necessities of SVE processes, and has many advantages over other fully equipped instrumentation, as a cost-effective device, with long-term monitoring stability.     

The Use of Mytilus Galloprovincialis Acetylcholinesterase and Glutathione S-Transferases Activities as Biomarkers of Environmental Contamination Along the Northwest Portuguese Coast

With the aim of using Mytilus galloprovincialis acetylcholinesterase (AChE) and glutathione S-transferases (GST) activities as biomarkers of environmental contamination in risk assessment studies along the northwest Portuguese coast, the objective of this study was to provide background information related to: (1) baseline values of these enzymatic activities both in reference and contaminated areas and their responsiveness as indicators of exposure to environmental contaminants; (2) the importance of seasonal variations of such biomarkers in M. galloprovincialis along this area. For this, the activity of these enzymes was seasonally determined in mussels collected from four sites, including a reference and three stations with different contamination sources along the referred area. Statistically significant differences on both enzymatic activities were found among the four sampling stations, at the four sampling periods. In comparison to the reference station, lower AChE and higher GST activity values were found in mussels collected in stations potentially contaminated by pesticides and domestic/industrial effluents and in mussels collected in the vicinity of an oil refinery and an industrial/mercantile harbour, respectively. The results obtained in this work highlighted the potential suitability of these biomarkers to be used as components of environmental monitoring programs in risk assessment studies along the northwest Portuguese coast. Since a seasonal variation in both enzymatic activities was found, the possible implications of such variability in the use of these enzymes as environmental biomarkers are also discussed.     

江苏生态环境无人机监测体系研究及初步应用

近年来,无人机技术趋于成熟并逐步得到广泛应用,成为一种新的环境监测平台。与传统监测方法相比,无人机监测平台具有快速、灵活、清晰、直观等突出优势。基于以往工作基础,研究并提出一种适用于江苏省的生态环境无人机监测体系,同时进一步讨论无人机在水、气、生态环境监测领域的业务应用思路。     

Rapid analysis of tile industry gaseous emissions by ion mobility spectrometry and comparison with solid phase micro-extraction/gas chromatography/mass spectrometry

The present paper reports on a rapid method for the analysis of gaseous emissions from ceramic industry, based on ion mobility spectrometry (IMS) as a means for on-site monitoring of volatile organic compounds (VOCs) produced during tile baking. IMS was calibrated with a set of reference compounds (i.e. ethyl acetate, ethanol, ethylene glycol, diethylene glycol, acetaldehyde, formaldehyde, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 1,3-dioxolane, 1,4-dioxane, benzene, toluene, cyclohexane, acetone, acetic acid) via air-flow permeation. The technique was tested on a laboratory-scale kiln and tiles prepared with selected glycol- and resin-based additives. Finally, the analytical method was applied to emissions from two industries in the Modena (Italy) ceramic area. The results of all experimental phases were compared to those obtained by solid phase micro-extraction/gas chromatography/mass spectrometry (SPME/GC/MS). IMS showed potential as a real-time monitoring device for quality assessment in ceramic industry emissions. IMS spectra, SPME/GC/MS data, relationship between additives/baking conditions and produced VOCs and advantages and limitations of both techniques will be discussed.     

Arsenic mobilization and attenuation by mineral-water interactions: implications for managed aquifer recharge

Managed aquifer recharge (MAR) has potential for addressing deficits in water supplies worldwide. It is also widely used for preventing saltwater intrusion, maintaining the groundwater table, and augmenting ecological stream flows, among many other beneficial environmental applications. However, field MAR sites have experienced arsenic mobilization from aquifer formation minerals due to induced changes in groundwater chemistry. To address this environmental concern, it is crucial to understand the potential sources and sinks impacting arsenic mobilization. This paper outlines important mineral-water interactions that can occur at MAR sites. Detailed information on minerals of concern, physiochemical processes for arsenic mobilization or attenuation, and the potential impact of microbial activity and hydrology on these processes is provided. Based on these mineral-water interactions, guidelines for predicting arsenic mobility are presented, and recommendations are made concerning MAR site monitoring. The review emphasizes important aspects in correlating interfacial reactions to reactive transport modeling and elucidating future challenges, a first step toward developing safer and more sustainable MAR operations.     

Designing an integrated environmental monitoring plan for land-based marine fish farms located at exposed and hard bottom coastal areas

The increase in aquaculture activities in the last few decades has not been accompanied by a corresponding increase in environmental controls and regulations. In this context, the application of environmental monitoring plans (EMPs) has become necessary to assess the environmental impact associated with fish farming wastes. The objective of this review paper is to evaluate the suitability of experimental and analytical procedures as monitoring tools for inclusion in EMPs for intensive land-based marine fish farms (LBMFFs). The strong hydrodynamics and, in particular, the lack of sediment on the rocky coasts where LBMFFs are usually located, greatly limit the monitoring tools that can be used. We propose EMPs that employ a weight-of-evidence approach to evaluate: contamination, trophic and toxic effects, and ecological integrity. Laboratory tests, in situ bioassays and field surveys of local species are presented as key tools for assessing the impact of LBMFFs on ecosystems. The δ(15)N signal along a spatial gradient is proposed for evaluating exposure to contaminants. Trophic effects can be determined by growth of transplanted macro- and microalgae. Toxic effects can be evaluated by responses at different levels of biological organization, including biochemical and histological changes, physiological alterations and survival, in species from different trophic levels. Fouling tests and analysis of community structures are recommended for assessing ecological integrity. This review contributes to the development of environmental controls for intensive LBMFFs, and for other activities that discharge wastewater to rocky shores.     

Classification of alluvial soils according to their potential environmental risk: a case study for Belgian catchments

Alluvial soils may represent important sinks of contaminants as a result of the deposition of contaminated sediments along the river by overbank flooding or after dredging. Because of the erosion of alluvial deposits or the release of contaminants from sediments, alluvial soils can also be a source of contamination. In this paper, a risk assessment for contaminated (alluvial) soils is presented. The approach, mainly based on physico-chemical soil characteristics, single extractions and leaching tests, is illustrated by means of a case study from four Belgian catchments. The extractions and leaching tests that were used have been validated by European testing programs and can provide valuable information for classifying the potential environmental risks of soils. Irrespective of the location, pH, organic carbon content and 'mobilisable' metal concentrations were the most important factors explaining 'mobile' metal concentrations in the alluvial soils. Additionally, the data of the physico-chemical soil characterization, extractions and leaching tests were combined with local and regional factors to classify the alluvial soils in different categories according to their actual and potential risk for the environment.     

The mini mobile environmental monitoring unit: a novel bio-assessment tool

This paper introduces a new bio-assessment tool, the mini-mobile environmental monitoring unit (MMU). The MMU is a portable, lightweight, energy-efficient, miniaturized laboratory that provides a low-flow system for on-site exposure of aquatic animals to local receiving waters in a protected, controllable environment. Prototypes of the MMU were tested twice in week-long studies conducted during the summers of 2008 and 2009, and in a 12-day study in 2010. In 2008, fathead minnows and polar organic chemical integrative samplers (POCIS) were deployed downstream from the Hastings, Nebraska wastewater treatment plant (WWTP), a waterway known to contain estrogenic contaminants in biologically active concentrations. In 2009, minnows and POCIS were deployed downstream, upstream and within the Grand Island, Nebraska WWTP, a site where the estrogenic contaminants had been detected, but were found at levels below those necessary to directly impact fish. In 2010, an advanced prototype was tested at the Sauk Center, Minnesota WWTP to compare its performance with that of traditional fish exposure methods including caged fish and static-renewal laboratory testing of effluent. Results from the prototype illustrate the capabilities of the MMU and offer an inexpensive monitoring tool to integrate the effects of pollutant sources with temporally varying composition and concentration.