Calibration and field performance of membrane-enclosed sorptive coating for integrative passive sampling of persistent organic pollutants in water

Membrane-enclosed sorptive coating (MESCO) is a miniaturised monitoring device that enables integrative passive sampling of persistent, hydrophobic organic pollutants in water. The system combines the passive sampling with solventless preconcentration of organic pollutants from water and subsequent desorption of analytes on-line into a chromatographic system. Exchange kinetics of chemicals between water and MESCO was studied at different flow rates of water, in order to characterize the effect of variable environmental conditions on the sampler performance, and to identify a method for in situ correction of the laboratory-derived calibration data. It was found that the desorption of chemicals from MESCO into water is isotropic to the absorption of the analytes onto the sampler under the same exposure conditions. This allows for the in situ calibration of the uptake of pollutants using elimination kinetics of performance reference compounds and more accurate estimates of target analyte concentrations. A field study was conducted to test the sampler performance alongside spot sampling. A good agreement of contaminant patterns and water concentrations was obtained by the two sampling techniques.     

Pesticide and agro-ecological transition: assessing the environmental and human impacts of pesticides and limiting their use

Environmental Science and Pollution Research -     

Environmental and economic impacts of decision-making at an arable farm: an integrative modeling approach

This study examines the dependency between physical and anthropogenic systems in arable farming. The dynamic simulation model, which has its methodological origins in the modeling traditions of environmental systems analysis and microsimulation, reproduces the mutual links between the physical flows (e.g. energy, materials, emissions, and products), the farmer as a decision-making agent, and structural conditions influencing the farm. In running the model, the intention is to answer the question: What are the impacts on profitability and the environment (i.e. greenhouse gas effects, eutrophication, acidification, and energy use) of variations in prices, subsidies, the farmer's environmental values, and the farmer's skill in making production allocation choices? The results of the model simulations indicate, for example, that in terms of economic performance, a farmer can choose between two relatively sustainable strategies--either to specialize in organic production (thereby benefiting from higher subsidies and output prices), or to focus on conventional cultivation and use of pesticides and fertilizers (thereby benefiting from large yields). Regarding environmental impacts, there was no clear-cut divide between organic and conventional farming due to difficulties in allocating the use of manure. This finding is essentially related to the choice of system boundary, which is thoroughly discussed in the paper.     

Comparison of a novel passive sampler to standard water-column sampling for organic contaminants associated with wastewater effluents entering a New Jersey stream

Four water samples collected using standard depth and width water-column sampling methodology were compared to an innovative passive, in situ, sampler (the polar organic chemical integrative sampler or POCIS) for the detection of 96 organic wastewater-related contaminants (OWCs) in a stream that receives agricultural, municipal, and industrial wastewaters. Thirty-two OWCs were identified in POCIS extracts whereas 9-24 were identified in individual water-column samples demonstrating the utility of POCIS for identifying contaminants whose occurrence are transient or whose concentrations are below routine analytical detection limits. Overall, 10 OWCs were identified exclusively in the POCIS extracts and only six solely identified in the water-column samples, however, repetitive water samples taken using the standard method during the POCIS deployment period required multiple trips to the sampling site and an increased number of samples to store, process, and analyze. Due to the greater number of OWCs detected in the POCIS extracts as compared to individual water-column samples, the ease of performing a single deployment as compared to collecting and processing multiple water samples, the greater mass of chemical residues sequestered, and the ability to detect chemicals which dissipate quickly, the passive sampling technique offers an efficient and effective alternative for detecting OWCs in our waterways for wastewater contaminants.     

A simplified method for sampling and analysis of high volume surface water for organic contaminants using XAD-2

A simple compressed-gas driven system for field processing and extracting water for subsequent analyses of hydrophobic organic compounds is presented. The pumping device is a pneumatically driven pump and filtration system that can easily clarify at 4 L/min. The extraction device uses compressed gas to drive filtered water through two parallel XAD-2 resin columns, at about 200 mL/min. No batteries or inverters are required for water collection or processing. Solvent extractions were performed directly in the XAD-2 glass columns. Final extracts are cleaned-up on Florisil cartridges without fractionation and contaminants analyzed by GC-MS. Method detection limits (MDLs) and recoveries for dissolved organic contaminants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides are reported along with results of surface water analysis for the San Francisco Bay, CA.     

Mixed models for assessing correlation in the presence of replication

The need to assess correlation in settings where multiple measurements are available on each of the variables of interest often arises in environmental science. However, this topic is not covered in introductory statistics texts. Although several ad hoc approaches can be used, they can easily lead to invalid conclusions and to a difficult choice of an appropriate measure of the correlation. Lam et al. approached this problem by using maximum likelihood estimation in cases where the replicate measurements are linked over time, but the method requires specialized software. We reanalyze the data of Lam et al. using PROC MIXED in SAS and show how to obtain the parameter estimates of interest with just a few lines of code. We then extend Lam et al.'s method to settings where the replicate measurements are not linked. Analysis of the unlinked case is illustrated with data from a study designed to assess correlations between indoor and outdoor measurements of benzene concentration in the air.     

A passive sampling method for radiocarbon analysis of atmospheric CO2 using molecular sieve

Radiocarbon (¹⁴C) analysis of atmospheric CO₂ can provide information on CO₂ sources and is potentially valuable for validating inventories of fossil fuel-derived CO₂ emissions to the atmosphere. We tested zeolite molecular sieve cartridges, in both field and laboratory experiments, for passively collecting atmospheric CO₂. Cartridges were exposed to the free atmosphere in two configurations which controlled CO₂ trapping rate, allowing collection of sufficient CO₂ in between 1.5 and 10 months at current levels. ¹⁴C results for passive samples were within measurement uncertainty of samples collected using a pump-based system, showing that the method collected samples with ¹⁴C contents representative of the atmosphere. δ¹³C analysis confirmed that the cartridges collected representative CO₂ samples, however, fractionation during passive trapping means that δ¹³C values need to be adjusted by an amount which we have quantified. Trapping rate was proportional to atmospheric CO₂ concentration, and was not affected by exposure time unless this exceeded a threshold. Passive sampling using molecular sieve cartridges provides an easy and reliable method to collect atmospheric CO₂ for ¹⁴C analysis.     

Modelling the fate of hydrophobic organic contaminants in a boreal forest catchment: A cross disciplinary approach to assessing diffuse pollution to surface waters

The fate of hydrophobic organic compounds (HOCs) in soils and waters in a northern boreal catchment was explored through the development of a chemical fate model in a well-characterised catchment system dominated by two land types: forest and mire. Input was based solely on atmospheric deposition, dominated by accumulation in the winter snowpack. Release from soils was governed by the HOC concentration in soil, the soil organic carbon fraction and soil-water DOC content. The modelled export of selected HOCs in surface waters ranged between 11 and 250 ng day⁻¹ during the snow covered period, compared to 200 and 9600 ng/d during snow-melt; highlighting the importance of the snow pack as a source of these chemicals. The predicted levels of HOCs in surface water were in reasonable agreement to a limited set of measured values, although the model tended to over predict concentrations of HOCs for the forested sub-catchment, by over an order of magnitude in the case of hexachlorobenzene and PCB 180. This possibly reflects both the heterogeneity of the forest soils and the complicated and changing hydrology experienced between the different seasons.     

A rapidly equilibrating, thin film, passive water sampler for organic contaminants; characterization and field testing

Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log K_EVA−W partition coefficients correlate well (r² = 0.87) with Log K_OW values for selected pesticides and polychlorinated biphenyls (PCBs) where Log K_EVA−W = 1.04 Log K_OW + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter.     

Suitability of passive sampling for the monitoring of pharmaceuticals in Finnish surface waters

The occurrence of five pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was studied by passive sampling and grab sampling in northern Lake Päijänne and River Vantaa. The passive sampling was performed by using Chemcatcher® sampler with a SDB-RPS Empore disk as a receiving phase. In Lake Päijänne, the sampling was conducted during summer 2013 at four locations near the discharge point of a wastewater treatment plant and in the years 2013 and 2015 at four locations along River Vantaa. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne determined by passive sampling ranged between 1.4–2.9 ng L^?1, 15–35 ng L^?1, 13–31 ng L^?1, 16–27 ng L^?1, and 3.3–32 ng L^?1, respectively. Similarly, the results in River Vantaa ranged between 1.2–40 ng L^?1, 15–65 ng L^?1, 13–33 ng L^?1, 16–31 ng L^?1, and 3.3–6.4 ng L^?1. The results suggest that the Chemcatcher passive samplers are suitable for detecting pharmaceuticals in lake and river waters.     

Local and distant residence times of contaminants in multi-compartment models. Part II: application to assessing environmental mobility and long-range atmospheric transport

In Part I, the concepts of inherent, local and distant residence times (DRTs) were reviewed as metrics of the extent to which chemical discharges or emissions in one region or box are transported to distant regions. In this second part, the concepts are applied to geographically relevant systems to illustrate their applicability to the assessment of chemicals for long-range transport potential (LRTP). It is shown that the relative ranking of chemicals as characterized by the DRT method is similar to that of the characteristic travel distance concept. A DRT source-receptor matrix is developed that can express the chemical-specific potential of source regions to contaminate a specific receptor region of concern such as the Arctic. The matrix can be modified to identify for a specific source region the likely destinations of emissions as well as to assess the relative vulnerability of regions in the global environment to contaminants of concern.     

Overview of passive Chemcatcher sampling with SPE pretreatment suitable for the analysis of NPEOs and NPs

The European Union Water Framework Directive (WFD; 2000/60/EC) is an important piece of environmental legislation that protects rivers, lakes, coastal waters and groundwaters (EC 2000). The implementation of the WFD requires the establishment and use of novel and low-cost monitoring programmes, and several methods, e.g. passive sampling, have been developed to make the sampling process more representative compared to spot sampling. This review considers passive sampling methods focusing mainly on a passive sampler named Chemcatcher®, which has been used for monitoring several harmful compounds in aquatic environments. Also, the sample treatment and analysis of nonylphenol ethoxylates (NPEOs) and nonylphenol (NPs) from water using solid phase extraction (SPE) is briefly summarized. The procedure of Chemcatcher passive sampling is quite similar to that of the SPE extraction since it concentrates the studied compounds from water as well. After sampling, the accumulated substances are extracted from the receiving phase of the sampler. The concentrations of NPEOs and NPs are currently monitored by taking conventional spot samples; SPE can be successfully used as a pretreatment procedure. Chemcatcher® passive sampling technique is a simple and useful monitoring tool and can be applied to new chemicals, such as NPEOs and NPs in aquatic environments.     

A holistic approach for optimal design of air quality monitoring network expansion in an urban area

This paper presents an objective methodology for determining the optimum number of ambient air quality stations in a monitoring network. The methodology integrates the multiple-criteria method with the spatial correlation technique. The pollutant concentration and population exposure data are used in this methodology in different ways. In the first stage, the Fuzzy Analytic Hierarchy Process (FAHP) with triangular fuzzy numbers (TFNs) is used to identify the most desirable monitoring locations. The network configuration is then determined on the basis of the concept of sphere of influences (SOIs). The SOIs are dictated by a predetermined cutoff value (r_c) in the spatial correlation coefficients (r) between the pollutant concentrations at the monitoring stations identified from first step and the corresponding concentrations at neighboring locations in the region. Finally, the optimal station locations are ranked by using combined utility scores gained from the first and second steps. The expansion of air quality monitoring network of Riyadh city in Saudi Arabia is used as a case study to demonstrate the proposed methodology.     

A numerical study on the vertical dispersion of passive contaminants from a continuous source in the atmospheric surface layer

A numerical solution of the diffusion equation is obtained for the vertical diffusion from a continuous source. The wind speed profile and the eddy diffusivity in this equation are expressed in terms of the surface-layer similarity relations obtained in the well-known Kansas experiments. A comparison is made with vertical concentration measurements obtained during the Prairie Grass and Porton experiments. The numerical results are in agreement with these experimental data.     

A review on management of chrome-tanned leather shavings: a holistic paradigm to combat the environmental issues

Raw hide/skins come to the tanners as a by-product of meat industry which is converted into value-added leather as product for fashion market. Leather manufacturing is a chemical process of natural biological matrix. It employs a huge quantity of water and inorganic and organic chemicals for processing and thereby discharges solid and liquid wastes into the environment. One of the potential solid wastes generated from leather industry is chrome-tanned leather shavings (CTLSs), and its disposal is increasingly becoming a huge challenge on disposal to tanners due to presence of heavy metal chromium. Hence, finding a sustainable solution to the CTLS disposal problem is a prime challenge for global tanners and researchers. This paper aims to the deeper review of various disposal methods on CTLS such as protein, chromium, and energy recovery processes and its utilization methodologies. Sustainable technologies have been developed to overcome CTLS solid wastes emanating from leather processing operations. Further, this review paper brings a broader classification of developed methodologies for treatment of CTLSs.     

Potential for cascading impacts of environmental change and policy on indigenous culture

Global environmental and societal changes threaten the cultures of indigenous peoples and local communities (IPLC). Despite the importance of IPLC worldviews and knowledge to sustaining human well-being and biodiversity, risks to these cultural resources are commonly neglected in environmental governance, in part because impacts can be indirect and therefore difficult to evaluate. Here, we investigate the connectivity of values associated with the relationship Ngātiwai (a New Zealand Māori tribe) have with their environment. We show that mapping the architecture of values-environment relationships enables assessment of how deep into culture the impacts of environmental change or policy can cascade. Our results detail how loss of access to key environmental elements could potentially have extensive direct and cascading impacts on the cultural values of Ngātiwai, including environmental responsibilities. Thus, considering only direct effects of environmental change or policy on cultural resources, or treating IPLC social-ecological relations simplistically, can severely underestimate threats to cultures.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-021-01670-3.     

Strategic environmental assessment of mining activities: A methodology for quantification of cumulative impacts on the air quality

Environmental impact assessments in Brazil have usually focused solely on project-related issues without considering the regional context. Although required by current environmental legislation, cumulative impact assessments have not been included in the overall environmental assessment of projects. However, in recent Strategic Environmental Assessment (SEA) studies of policies, plans, and programs undertaken on a voluntary basis in support of the decision-making process, this kind of assessment has been performed especially with respect to air quality. This paper presents the application of a methodology for the quantification of cumulative impacts on air quality under high uncertainty caused by various mining activities in a single region that is recommended for SEA studies. In this way, the methodology presented here is suitable for areas lacking detailed modeling information. The developed approach uses a relatively simplified mathematical model, lowering information gathering costs and requiring little processing time. The application of the methodology is illustrated in the case of a SEA of the Corumbá Mining and Industrial Complex Development Program. Despite the lack of data needed for a minimum characterization of conditions of the area surrounding the region modeled, the quantification of impact cumulativeness on air quality has played an important role in the context of the SEA.     

Use of passive sampling devices for monitoring and compliance checking of POP concentrations in water

Background

The state of the art of passive water sampling of (nonpolar) organic contaminants is presented. Its suitability for regulatory monitoring is discussed, with an emphasis on the information yielded by passive sampling devices (PSDs), their relevance and associated uncertainties. Almost all persistent organic pollutants (POPs) targeted by the Stockholm Convention are nonpolar or weakly polar, hydrophobic substances, making them ideal targets for sampling in water using PSDs. Widely used nonpolar PSDs include semi-permeable membrane devices, low-density polyethylene and silicone rubber.

Results and discussion

The inter-laboratory variation of equilibrium partition constants between PSD and water is mostly 0.2?C0.5 log units, depending on the exact matrix used. The sampling rate of PSDs is best determined by using performance reference compounds during field deployment. The major advantage of PSDs over alternative matrices applicable in trend monitoring (e.g. sediments or biota) is that the various sources of variance including analytical variance and natural environmental variance can be much better controlled, which in turn results in a reduction of the number of analysed samples required to obtain results with comparable statistical power.

Conclusion

Compliance checking with regulatory limits and analysis of temporal and spatial contaminant trends are two possible fields of application. In contrast to the established use of nonpolar PSDs, polar samplers are insufficiently understood, but research is in progress to develop PSDs for the quantitative assessment of polar waterborne contaminants. In summary, PSD-based monitoring is a mature technique for the measurement of aqueous concentrations of apolar POPs, with a well-defined accuracy and precision.     

Calibration and field application of a solvent-based cellulose membrane passive sampling device for the monitoring of polar herbicides

A passive sampler device selective for hydrophilic analytes was constructed from cellulose membrane (40microm thickness) pre-stained with ruthenium red for 96-168h to impede degradation of the cellulose. The sampling device consisted of pre-stained cellulose membrane tubing containing a binary mixture of the solvents 1-dodecanol and 2,2,4-trimethylpentane as the sequestering medium. A laboratory flow-through system was used to investigate the rates of uptake of herbicides into the solvent mixture of the device and their release. The target herbicides were diuron, atrazine, metolachlor and molinate. Uptake of the herbicides into the solvent mixture of the cellulose membrane device was linear for up to 22 days, and daily sampling rates were determined. Release half-lives from the solvent mixture of the sampling device varied from 14 days for diuron, 15 days for atrazine, 84 days for metolachlor and 28 days for molinate. A field study was undertaken to determine if herbicide concentrations in agricultural drainage water derived from the passive sampler devices deployed for periods from 7 to 22 days, using the laboratory-derived sampling rates, would compare closely with time-weighted average herbicide concentrations determined from extractions of daily composite water samples. The concentrations of diuron, atrazine, metolachlor and molinate determined using the cellulose membrane devices were within twofold of the cumulated mean of the daily drainage water extractions.     

Updated methods for assessing the impacts of nearby gas drilling and production on neighborhood air quality and human health

An explosive growth in natural gas production within the last decade has fueled concern over the public health impacts of air pollutant emissions from oil and gas sites in the Barnett and Eagle Ford shale regions of Texas. Commonly acknowledged sources of uncertainty are the lack of sustained monitoring of ambient concentrations of pollutants associated with gas mining, poor quantification of their emissions, and inability to correlate health symptoms with specific emission events. These uncertainties are best addressed not by conventional monitoring and modeling technology, but by increasingly available advanced techniques for real-time mobile monitoring, microscale modeling and source attribution, and real-time broadcasting of air quality and human health data over the World Wide Web. The combination of contemporary scientific and social media approaches can be used to develop a strategy to detect and quantify emission events from oil and gas facilities, alert nearby residents of these events, and collect associated human health data, all in real time or near-real time. The various technical elements of this strategy are demonstrated based on the results of past, current, and planned future monitoring studies in the Barnett and Eagle Ford shale regions.

Implications: Resources should not be invested in expanding the conventional air quality monitoring network in the vicinity of oil and gas exploration and production sites. Rather, more contemporary monitoring and data analysis techniques should take the place of older methods to better protect the health of nearby residents and maintain the integrity of the surrounding environment.