Comparison of trip average in-vehicle and exterior CO determinations by continuous and grab sampling using an electrochemical sensing method

In air quality monitoring studies, continuous sampling is capable of reflecting real time variation of gas levels, however, with a margin of uncertainty related to the response time of the sensor and to the speed of concentration fluctuation. In contrast, grab sampling allows the determination of average gas concentration over the whole sampling period eliminating thus the uncertainties associated with the continuous method. As studies of in-vehicle carbon monoxide (CO) exposure often show rapidly fluctuating CO levels and are increasingly using the continuous electrochemical sensing method, the present activity aims at validating the suitability of the latter method for this monitoring task. For this purpose, an electrochemical CO sensing monitor was used to continuously monitor CO level inside and outside of a vehicle moving in an urban area, and to analyze the content of concomitantly taken grab samples. Trip-average CO levels measured using the two testing methods were compared. For CO levels higher than the instrument detection limit (1 ppm), the observed percent difference between continuous and grab sampling results varied within a fairly acceptable range (0.6–15.4%). The regression of continuous sampling data against grab sampling data revealed an average error of 6.9%, indicating the suitability of the continuous electrochemical method for monitoring in-vehicle and exterior average CO concentration under typical urban traffic conditions.     

A comparison of river water quality sampling methodologies under highly variable load conditions

When river water quality fluctuates over relatively short periods of time with respect to the sampling frequency, the collection of grab samples may be inappropriate for characterising average water quality. This paper presents the results of a water quality monitoring study carried out on a stretch of the river Lambro (northern Italy) dominated by a periodically overloaded sewage treatment works (STW) located near its upstream end. Water quality was strongly influenced by a pronounced diurnal cycle in pollutant loads caused by the regular emission of untreated waste water during periods of high domestic flow (daytime). Two different sampling techniques were employed: grab sampling and 24-h composite sampling using automatic samplers. Samples were collected at the plant overflow and at several sites along the river and analysed for two common ingredients of household detergents, linear alkylbenzene sulphonate (LAS) and boron (B) and for routine water quality variables. The results obtained show that: (1) The diurnal variability of point-source-derived chemical concentrations in the river downstream of the undersized STW increased with increasing removal efficiency in sewage treatment. (2) The shape of the diurnal concentration signal remained relatively intact for a considerable distance downstream of the STW for several water quality variables, suggesting that hydrodynamic dispersion plays a relatively minor role in controlling concentration patterns in this river. (3) In-stream degradation of LAS was consistent with first order kinetics with a rate constant of 0.05-0.06 h(-1). (4) Grab sampling is a relatively inefficient methodology for capturing mean concentrations for rivers subjected to highly variable loads, especially when it is restricted to office hours. The inefficiency of grab sampling is more marked for substances (e.g. LAS) which are effectively removed during sewage treatment than for substances which are not. (5) For LAS, diurnal variability in the concentration signal decreases with distance downstream, making grab sampling an increasingly reliable methodology for estimating mean concentrations. (6) 24-h composite sampling is an efficient way of eliminating the effect of diurnal variations in load strength.     

Fluorescent dye imaging of the volume sampled by single well forced-gradient tracer tests evaluated in a laboratory-scale aquifer physical model

This study presents a new method to visualise forced-gradient tracer tests in 2-D using a laboratory-scale aquifer physical model. Experiments were designed to investigate the volume of aquifer sampled in vertical dipole flow tracer tests (DFTT) and push-pull tests (PPT), using a miniature monitoring well and straddle packer arrangement equipped with solute injection and recovery chambers. These tests have previously been used to estimate bulk aquifer hydraulic and transport properties for the evaluation of natural attenuation and other remediation approaches. Experiments were performed in a silica glass bead-filled box, using a fluorescent tracer (fluorescein) to deduce conservative solute transport paths. Digital images of fluorescein transport were captured under ultraviolet light and processed to analyse tracer plume geometry and obtain point-concentration breakthrough histories. Inorganic anion mixtures were also used to obtain conventional tracer breakthrough histories. Concentration data from the conservative tracer breakthrough curves was compared with the digital images and a well characterised numerical model. The results show that the peak tracer breakthrough response in dipole flow tracer tests samples a zone of aquifer close to the well screen, while the sampling volume of push-pull tests is limited by the length of the straddle packers used. The effective sampling volume of these single well forced-gradient tests in isotropic conditions can be estimated with simple equations. The experimental approach offers the opportunity to evaluate under controlled conditions the theoretical basis, design and performance of DFTTs and PPTs in porous media in relation to measured flow and transport properties.     

Grab and passive sampling applied to pesticide analysis in the São Lourenço river headwater in Campo Verde – MT,Brazil

In this study, the quality of surface water in the headwaters of São Lourenço River in Mato Grosso, Brazil, was evaluated in relation to contamination by pesticides. For this purpose, samples were collected between December 2015 and June 2016 by grab sampling and by passive sampling using an integrative polar organic compound sampler installed in the field during four 14-day cycles between March and June 2016. The analyses were performed by gas chromatography (CG/MS) and by liquid chromatography (UPLC-MS/MS). The results showed the detection of two pesticides (atrazine and pyraclostrobin) of the five analyzed by passive sampling and eight active principles among the 20 analyzed (malathion, diuron, carbofuran, carbendazim, trifluralin, imidacloprid, metolachlor, and acetamiprid) by grab sampling. The detection of 10 pesticides, even almost a decade after the beginning of a recovery process of the ciliary forest, confirms the headwaters' vulnerability to these contaminants and passive sampling proved to be an important tool in capturing small concentrations of pesticides constituting an interesting complement to grab sampling.     

Comparison between the polar organic chemical integrative sampler and the solid-phase extraction for estimating herbicide time-weighted average concentrations during a microcosm experiment

Polar organic chemical integrative samplers (POCIS) were exposed for 9 days in two different microcosms that contained river waters spiked with deethylterbuthylazine, terbuthylazine and isoproturon. The experiment was performed with natural light and strong turbulence (flow velocities of about 15-50cms(-1)) for reproducing natural conditions. The concentrations were kept relatively constant in the first microcosm (2.6-3.6mugl(-1)) and were variable in the second microcosm (peak concentrations ranged from 15 to 24mugl(-1) during the 3 day pulse phase). The time-weighted average (TWA) concentrations were determined with both POCIS and repetitive grab sampling followed by solid-phase extraction. The results showed a systematic and significant overestimation of the TWA concentrations with the POCIS most probably due to the use of sampling rates derived under low flow scenario. The results showed also that peak concentrations of pollutants are fully integrated by this passive sampler. Even if the POCIS should not provide very accurate concentration estimates without the application of adequate sampling rate values or the use of performance reference compounds, it can be a really useful tool for detecting episodic or short-term pollution events (e.g. increased herbicide concentrations during a flood), which may be missed with classical and low frequency grab sampling.     

Food-service establishment wastewater characterization.

Food-service establishments that use on-site wastewater treatment systems are experiencing pretreatment system and/or drain field hydraulic and/or organic overloading. This study included characterization of four wastewater parameters (five-day biochemical oxygen demand [BOD5]; total suspended solids [TSS]; food, oil, and grease [FOG]; and flow) from 28 restaurants located in Texas during June, July, and August 2002. The field sampling methodology included taking a grab sample from each restaurant for 6 consecutive days at approximately the same time each day, followed by a 2-week break, and then sampling again for another 6 consecutive days, for a total of 12 samples per restaurant and 336 total observations. The analysis indicates higher organic (BOD5) and hydraulic values for restaurants than those typically found in the literature. The design values for this study for BOD5, TSS, FOG, and flow were 1523, 664, and 197 mg/L, and 96 L/day-seat respectively, which captured over 80% of the data collected.     

Development and demonstration of a free surface flow-dependent sampling technology

Statistical assessment of water quality data, obtained at the South Florida Water Management District (West Palm Beach, Florida) S-65E structure, illustrated significant differences and inconsistency in nutrient concentrations (Daas and Ebadian, 2003). The evaluation showed that currently used water sampling techniques are inadequate because of deficiencies in functionality and sensitivity to flow conditions at the structure. Moreover, the study indicated the need for a more precise sampling technology, which would consider variations in the velocity profile across the water column during the sampling process. Therefore, a new prototype sampling technology was designed and tested in a pilot open channel. The new sampler had the capability to collect discrete aliquot volumes of water samples that are proportional to the corresponding point velocity at each of these depths. The discrete aliquot volumes were blended to provide an integrated sample that captures the variations in the velocity profile.     

Two sampling strategies for an overview of pesticide contamination in an agriculture-extensive headwater stream

Two headwaters located in southwest France were monitored for 3 and 2 years (Auvézère and Aixette watershed, respectively) with two sampling strategies: grab and passive sampling with polar organic chemical integrative sampler (POCIS). These watersheds are rural and characterized by agricultural areas with similar breeding practices, except that the Auvézère watershed contains apple production for agricultural diversification and the downstream portion of the Aixette watershed is in a peri-urban area. The agricultural activities of both are extensive, i.e., with limited supply of fertilizer and pesticides. The sampling strategies used here give specific information: grab samples for higher pesticide content and POCIS for contamination background noise and number of compounds found. Agricultural catchments in small headwater streams are characterized by a background noise of pesticide contamination in the range of 20–70 ng/L, but there may also be transient and high-peak pesticide contamination (2000–3000 ng/L) caused by rain events, poor use of pesticides, and/or the small size of the water body. This study demonstrates that between two specific runoff events, contamination was low; hence the importance of passive sampler use. While the peak pesticide concentrations seen here are a toxicity risk for aquatic life, the pesticide background noise of single compounds do not pose obvious acute nor chronic risks; however, this study did not consider the risk from synergistic “cocktail” effects. Proper tools and sampling strategies may link watershed activities (agricultural, non-agricultural) to pesticides detected in the water, and data from both grab and passive samples can contribute to discussions on environmental effects in headwaters, an area of great importance for biodiversity.     

The performance of passive flow monitors and phosphate accumulating passive samplers when exposed to pulses in external water flow rate and/or external phosphate concentrations

Passive samplers are typically calibrated under constant flow and concentration conditions. This study assessed whether concentration and/or flow pulses could be integrated using a phosphate passive sampler (P-sampler). Assessment involved three 21-day experiments featuring a pulse in flow rate, a pulse of filterable reactive phosphate (FRP) concentration and a simultaneous concentration and flow pulse. FRP concentrations were also determined by parallel grab sampling and the P-sampler calibrated with passive flow monitors (PFMs) and direct measurement of flow rates. The mass lost from the PFM over the deployment periods predicted water velocity to within 5.1, 0.48 and 7.1% when exposed to a flow rate pulse (7.5-50 cm s⁻¹), concentration pulse (5-100 μg P L⁻¹), or both simultaneously. For the P-sampler, good agreement was observed between the grab and passive measurements of FRP concentration when exposed to a pulse in flow (6% overestimation) or concentration (2% underestimation).     

Toxicity of urban highway runoff in Shanghai to Zebrafish (Danio rerio) embryos and luminous bacteria (Vibrio qinghaiensis.Q67)

Pollution from urban highway runoff has been identified as one of the major causes of the deterioration of receiving water quality. The purpose of this study is to assess the toxicity of urban storm water samples in Shanghai using the zebrafish (Danio rerio) embryo test and the bacterial luminescence (Vibrio qinghaiensis) assay. The toxicity of highway runoff from seventeen storm events was investigated in both grab and composite samples. Zebrafish embryos were exposed to the runoff samples and development parameters including lethality, spontaneous movements in 20 s, heart beat rate, hatching rate, and abnormality of zebrafish embryos were observed after 24, 48, 72, and 96 h of exposure. Inhibition rates of luminescence intensity were also recorded. The results showed that in the zebrafish embryo toxicity tests, both grab and composite samples increased the lethality, reduced the percentage with spontaneous movements and heart beats, inhibited the hatching of embryos, and induced morphological abnormalities. In the Vibrio qinghaiensis toxicity test, all the grab samples inhibited the luminescence, while some of the composite samples promoted it, which indicated that different types of toxicants might have been affecting the species. The multivariate statistics analysis indicated that heavy metal (zinc, manganese, and copper) and PAHs might mainly contribute to the toxicity of runoff samples.     

Development of solid phase adsorption toxin tracking (SPATT) for monitoring anatoxin-a and homoanatoxin-a in river water

Sampling and monitoring for cyanotoxins can be problematic as concentrations change with environmental and hydrological conditions. Current sampling practices (e.g. grab samples) provide data on cyanotoxins present only at one point in time and may miss areas or times of highest risk. Recent research has identified the widespread distribution of anatoxin-producing benthic cyanobacteria in rivers highlighting the need for development of effective sampling techniques. In this study we evaluated the potential of an in situ method known as solid phase adsorption toxin tracking (SPATT) for collecting and concentrating anatoxin-a (ATX) and homoanatoxin-a (HTX) in river water. Fifteen different adsorption substrates were screened for efficiency of ATX uptake, nine of which retained high proportions (>70%) of ATX. Four substrates were then selected for a 24-h trial in a SPATT bag format in the laboratory. The greatest decrease in ATX in the water was observed with powdered activated carbon (PAC) and Strata-X (a polymeric resin) SPATT bags. A 3-d field study in a river containing toxic benthic cyanobacterial mats was undertaken using PAC and Strata-X SPATT bags. ATX and HTX were detected in all SPATT bags. Surface grab samples were taken throughout the field study and ATX and HTX were only detected in one of the water samples, highlighting the limitations of this currently used method. Both Strata-X and PAC were found to be effective absorbent substrates. PAC has the advantage that it is cheap and readily available and appears to continue to sorb toxins over longer periods than Strata-X. SPATT has the potential to be integrated into current cyanobacterial monitoring programmes and would be a very useful and economical tool for early warning of ATX and HTX contamination in water.     

Visibility Measurements lo National Parks In the Western United States

Abstract

Existing quantitative standards/guidelines for fungi in indoor air issued by governmental agencies are based primarily on baseline data (rather than health effects data), and are either absolute (numerical) or relative (indoor/outdoor comparisons) or a combination of the two. The Russian Federation is the only governmental agency that has binding quantitative regulations for bioaerosols. Recommended guidelines have been proposed or sponsored by North American and European governmental agencies and private professional organizations. A considerable number of frequently cited guidelines have been proposed by individuals based either on baseline data or on personal experience. Quantitative standards/guidelines range from less than 100 CFU/ m3 to greater than 1000 CFU/m3 (total fungi) as the upper limit for non-contaminated indoor environments.

Major issues with existing quantitative standards and guidelines are the lack of connection to human dose/response data, reliance on short term grab samples analyzed only by culture, and the absence of standardized protocols for data collection, analysis, and interpretation. Urgent research needs include the study of human responses to specific fungal agents, development and widespread use of standard protocols using currently available sampling methodologies, and the development of long term, time-discriminating personal samplers that are inexpensive, easy to use, and amenable to straightforward, relevant analysis.     

Determination of major natural and anthropogenic source profiles for particulate matter and trace elements in Izmir, Turkey

Samples of PM10 and PM2.5 were collected from several natural and anthropogenic sources using in-stack cyclone, grab sampling/resuspension chamber and ambient air samplers. The chemical characterization of the samples was achieved containing Al, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V and Zn using an inductively coupled plasma-optical emission spectrometer (ICP-OES). The elemental fractions (weight percent by mass), standard deviations and uncertainties were reported. The elemental compositions of PM emitted from mineral industries and cement kiln were dominated by terrestrial elements, particularly Ca, whereas the profile of top-soil mainly contained Al and Ca. The profiles of industrial sources were generally typical for related ones; however, significant differences were obtained for some of them. Similarly, the profiles of fuel burning emissions have significant differences compared to profiles obtained all around the world.     

Air sampling and analysis of volatile organic compounds with solid phase microextraction

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.     

Sediment quality in littoral regions of the Gulf of Cádiz: a triad approach to address the influence of mining activities

To evaluate sediment quality in different areas in the Gulf of Cádiz affected by mining activities, an integrative approach to assessment was used: the Sediment Quality Triad (SQT). Sediment samples were collected at six stations and subjected to replicated sediment acute and chronic toxicity tests, and comprehensive sediment chemistry analyses. Organisms collected synoptically at the same stations were analyzed for histopathological lesions and chemical concentrations in their tissues to determine 'in situ' alteration and bioavailability, in place of benthic community structure. The results obtained for each component were linked to the SQT using different methodologies of interpretation and expression of the integrated approach: (a) multivariate analysis, (b) significant statistical differences compared to the reference stations, (c) ANOVA-based pie charts, and (d) classical methods using triangles and the SQT index of pollution. SQT results indicated that the highest pollution was mainly associated with metals from mining activities and polyaromatic hydrocarbons in the Ría of Huelva. The use of histopathological measures and bioaccumulation of metals, improved the characterization of 'gray areas' of pollution and in the determination of the bioavailability of metals.     

Site-specific water quality guidelines: 2. Development of a water quality regulation framework for pulse exposures of mine water discharges at a uranium mine in northern Australia

The Ranger Uranium Mine, in northern Australia, is monitored by the Supervising Scientist Division (SSD) of the Australian Government to ensure that it does not impact on the highly valued aquatic ecosystems of Kakadu National Park. In 2010, the SSD adopted the continuous monitoring of electrical conductivity (EC) and turbidity, in combination with event-triggered automated grab samples, as its primary water quality monitoring method. The continuous monitoring of EC has shown that mine discharges typically occur over short-term ‘pulse’ durations of minutes to hours. Given that magnesium (Mg) is the most likely mine-derived solute to approach or exceed the applicable water quality limit value, the focus has been on developing a pulse exposure assessment framework for Mg, as represented by its proxy EC, which is tracked by the continuous monitoring system. This study presents a possible ecotoxicologically derived Mg pulse exposure limit and trigger regulation framework for Magela and Gulungul Creeks and an assessment of historic continuous monitoring EC data from these creeks. This framework demonstrates potential to supersede the current EC guideline and associated trigger levels, which are statistically derived from historic grab sample data.     

Comments on the NAS Report: Odors From Stationary and Mobile Sources

ABSTRACT

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.     

Transient and Frequency Response of Air Quality Monitors

Results of dynamic or transient tests and steady state calibration of carbon monoxide and sulfur dioxide continuous air quality monitors are reported. Standard gases and permeation tubes were used to establish low level concentrations bpth for the steady-state calibration and the dynamic testing. The steady-state calibration was in excellent agreement with results obtained from grab samples of the calibration gas stream taken with standard gas bubblers and analyzed by the West and Gaeke procedure. Such tests have been carried out by other investigators with similar results. The important contribution of this paper lies in the application of dynamic testing techniques developed by the senior author and co-workers to determine the transient and frequency response characteristics of these air quality monitors.     

Dynamic air sampling of volatile organic compounds using solid phase microextraction

A new dynamic air sampling system was devised and evaluated in conjunction with solid phase microextraction (SPME) fiber materials for extracting odor-causing volatile organic compounds (VOCs) present in swine building environments. Utilizing a standard solution consisting of 11 compounds (i.e., volatile fatty acids, indoles, and phenol), sampling times, volumes, and flow rates were adjusted to establish optimal extraction conditions. Results indicated that the sampling system was effective with the Carboxen/Polydimethylsiloxane (CAR/PDMS) fiber in extracting all 11 standard compounds. The best sampling conditions for the extraction were a 100-mL sampling vial subjected to a continuous flow of 100 mL/min for 60 min. The gas chromatographic analysis showed that the reproducibility was within acceptable ranges for all compounds (RSD=4.24-17.26% by peak areas). In addition, field tests revealed that the sampling system was capable of detecting over 60 VOCs in a swine house whose major components were identified by gas chromatography-mass spectrometry (GC-MS) and by their retention times as volatile fatty acids, phenols, indole, and skatole. The field tests also showed that considerably different levels of VOCs were present in various parts of the swine building.     

Statistical analysis of heavy metal data from municipal waste incineration residues

Heavy Metal data from a measurement program at a municipal incinerator in Vienna, Austria are analysed. The experimental design had a nested structure, and analysis of variance is used to break down the total variability into several components; (1) variability between mean hourly concentrations, (2) variability between mean sample concentrations within intervals of an hour and (3) variability due to “measurement” errors. Results of a pre-experiment show, that if grab samples are taken, within hour variation is dominant. The results of analysis of variance were used to calculate an optimal number of samples, which ensure a predetermined accuracy for the mean concentrations. In two main measuring periods with different incinerated waste types, slag and fly ash (ESP dust and boiler ash) data are produced and analysed. For both slag and fly ash, significant differences in measures of location and dispersion between the data sets of the main experiment are found. This proves, that differences in the chemical set up of waste can be detected via incineration residues.