Sorption kinetics of parent and substituted PAHs for low-density polyethylene（LDPE）:Determining their partition coefficients between LDPE and water(KLDPE) for passive sampling

Low-density polyethylene(LDPE)has been widely used as a sorbent for passive sampling of hydrophobic organic contaminants(HOCs)in aquatic environments.However,it has seen only limited application in passive sampling for measurement of freely dissolved concentrations of parent and substituted PAHs(SPAHs),which are known to be toxic,mutagenic and carcinogenic.Here,the 16 priority PAHs and some typical PAHs were selected as target compounds and were simultaneously determined by gas chromatography–mass spectrometer(GC–MS).Some batch experiments were conducted in the laboratory to explore the adsorption kinetics of the target compounds in LDPE membranes.The results showed that both PAHs and SPAHs could reach equilibrium status within19–38 days in sorption kinetic experiments.The coefficients of partitioning between LDPE film(50μm thickness)and water(KLDPE)for the 16 priority PAHs were in good agreement with previously reported values,and the values of KLDPEfor the 9 SPAHs are reported in this study for the first time.Significant linear relationships were observed,i.e.,log KLDPE=0.705×log KOW+1.534 for PAHs(R^2=0.8361,p<0.001)and log KLDPE=0.458×log KOW+3.092 for SPAHs(R^2=0.5609,p=0.0077).The selected LDPE film was also proven to meet the condition of"zero sink"for the selected target compounds.These results could provide basic support for the configuration and in situ application of passive samplers.

Sources and Trends of Persistent Organic Pollutants at Three Passive Monitoring Sites in South Africa

The Stockholm Convention on Persistent Organic Pollutants (SCPOPs) is an international treaty that operates under the patronage of the United Nations (UN) to control certain chemicals that are considered persistent organic pollutants (POPs). They are of great concern because of their adverse effects on human health and the environment. Exposure to POPs may lead to cancer, infertility, respiratory infections, and other health complications. It is therefore critical to study the degree of human and environmental exposure to these POPs. Passive air sampling was conducted in South Africa to evaluate the presence and trends of persistent organic pollutants at Barberspan (rural agricultural), Vanderbijl Park (urban industrial) and Molopo Nature Reserve (isolated nature reserve). Samples were collected in 2012. Passive air samplers using poly were used for sampling. The Buchi System B-811 automatic extractor was used to analyze for dichloro-diphenyl-trichlorethane (DDT), pentachlorobenzene (PeCB), hexechlorobenzene (HCB) polychlorinated biphenyls (PCBs) and hexachlorocyclohexane (HCH). Sampling was conducted for a period of one year. POPs concentrations were generally low at all sites, but Vanderbijl Park had the highest concentrations. Seasonal changes in concentrations were much the same at the three sites with temperatures and wind patterns being major factors. The presence of these chemicals in Molopo Nature Reserve and Barberspan is evidence of long range transportation over dry semi desert areas. Back-trajectories indicate possible sources, including areas where DDT is used for malaria control. The presence of POPs is areas they have never been in use poses health and environmental risks in these areas.

A passive sampler for synchronously measuring inorganic and organic pollutants in sediment porewater:Configuration and field application

In situ measurement of multiple pollutants coexisting in sediment porewater is an essential step in comprehensively assessing the bioavailability and risk of pollutants,but to date,this needs to be better developed.In this study,a passive sampler,consisting of an“I-shaped”supporting frame and inorganic/organic sampling units,incorporating equilibrium dialysis theory and kinetic/equilibrium sorption principle,was developed for the synchronous measurement of inorganic(e.g.,phosphorus and metal(loid)s)and organic pollutants(e.g.,parent and substituted PAHs).The equilibrium time and sampling rates were explored in laboratory tests to support in situ application.Profiles of pollutants in porewater within a vertical resolution of centimeters,i.e.,1 cm and 2 cm for inorganic and organic pollutants,respectively,were obtained by field deployment of the sampler for further estimation of diffusive fluxes across the sediment-water interface.The results suggested that the role of sediments for a specific pollutant may change(e.g.,from“sink”to“source”)during the sampling time.This study demonstrated the feasibility of synchronous measurement of inorganic and organic pollutants in sediment porewater by the passive sampler.In addition,it provided new insight for further investigation into the combined pollution effects of various pollutants in sediments.

Nontarget screening using passive air and water sampling with a level Ⅱ fugacity model to identify unregulated environmental contaminants

It is thought that there are many unregulated anthropogenic chemicals in the environment.For risk assessment of chemicals, it is essential to estimate the predicted environmental concentrations. As an effort of identifying residual organic contaminants in air and water in Korea, nontarget screening using two-dimensional gas chromatography time-of-flight mass spectrometry(GC × GC-TOFMS) was conducted at 10 sites using polyurethane foam passive air sampler and at 6 sites using polydimethyl siloxane(PDMS) passive water sampler in three different seasons in 2014. More than 600 chemical peaks were identified satisfying the identification criteria in air and water samples, respectively, providing a list for further investigation. Chemical substances with reported national emission rates in2014(n = 149) were also screened for potential existence in the environment using a level Ⅱ fugacity model. Most of chemical substances classified as not detectable were not identified with detection frequency greater than 20% by nontarget screening, indicating that a simple equilibrium model has a strong potential to be used to exclude chemicals that are not likely to remain in the environment after emissions from targeted monitoring.

Impact of environmental factors on the sampling rate ofβ-blockers and sulfonamides from water by a carbon nanotube-passive sampler

Passive techniques are a constantly evolving approach to the long-term monitoring of micropollutants,including pharmaceuticals,in the aquatic environment.This paper presents,for the first time,the calibration results of a new CNTs-PSDs(carbon nanotubes used as a sorbent in passive sampling devices)with an examination of the effect of donor phase salinity,water pH and the concentration of dissolved humic acids(DHAs),using both ultrapure and environmental waters.Sampling rates(R_(s))were determined for the developed kinetic samplers.It has been observed that the impact of the examined environmental factors on the R_(s) values strictly depends on the type of the analytes.In the case ofβ-blockers,the only environmental parameter affecting their uptake rate was the salinity of water.A certain relationship was noted,namely the higher the salt concentration in water,the lower the Rs values ofβ-blockers.In the case of sulfonamides,water salinity,water pH 7-9 and DHAs concentration decreased the uptake rate of these compounds by CNTs-PSDs.The determined Rs values differed in particular when the values obtained from the experiments carried out using ultrapure water and environmental waters were compared.The general conclusion is that the calibration of novel CNTs-PSDs should be carried out under physicochemical conditions of the aquatic phase that are similar to the environmental matrix.

Comparisons of indoor active and passive air sampling methods for emerging and legacy halogenated flame retardants in Beijing, China offices

One active and two passive air sampling configurations were deployed simultaneously in three offices in Beijing,China to test their comparability for sampling emerging and legacy halogenated flame retardants spanning a large range of octanoleair partition coefficients(KOA).Sampling in each office was carried out for three consecutive 28-day periods in the spring-summer of 2013.The active sampler was run for 2.5 h at different times every day for 28 days to parallel the passive samplers and sample a total volume comparable to that sampled by the passive samplers(~20 m^3).At the end of each 28-day sampling period,a separate active air sample was taken by running the sampler pump continuously for about 2.5 days.The comparability of measured concentrations varied between the air sampling configurations and for different compounds.The predominant compound measured in nearly all samples was BDE-209,a compound known to have heavy use in China.Several emerging flame retardants were also detected including DBE-DBCH,PBT,HBB,DDC-CO,and DBDPE.Very little of the tetra-hexabrominated BDEs associated with the technical PentaBDE product was observed.

Levels and Sources of Atmospheric Polycyclic Aromatic Hydrocarbons Surrounding an Oil Refinery in Curacao

This research measured ambient levels of polycyclic aromatic hydrocarbons (PAHs) surrounding a petrochemical complex on the island of Curacao using passive air sampling. In addition, source elucidation of PAHs was conducted using concentration profiles, distribution profiles, binary diagnostic ratios and factor analysis. Passive air samplers with polyurethane foam collection disks (PAS-PUFs) were deployed in 2011 (n = 43) and in 2014 (n = 30) to evaluate the extent of the emission plume as well as spatial and temporal differences in ambient PAH concentrations. In general, ambient PAH concentrations in Curacao were consistent with other urban and industrialized regions of the world;however, the levels measured downwind of Isla Refineriá petrochemical complex were among some of the highest reported ambient PAHs globally. Ambient PAH concentrations ranged from 1.2 to 790 ng/m3 in 2011 and 27 to 660 ng/m3 in 2014, demonstrating no temporal differences. However, significant spatial differences were detected between samples collected upwind and downwind of the petrochemical complex. Significantly higher ambient PAH concentrations were found in the samples collected downwind of the petrochemical complex compared to those upwind in 2014

Diffusive gradients in thin films(DGT) probe for effectively sampling of per-and polyfluoroalkyl substances in waters and sediments

The passive sampling technique, diffusive gradients in thin films(DGT) has attracted increasing interests as an in-situ sampler for organic contaminants including per-and polyfluoroalkyl substances(PFAS). However, its effectiveness has been questioned because of the small effective sampling area(3.1 cm^(2)). In this study, we developed a DGT probe for rapid sampling of eight PFAS in waters and applied it to a water-sediment system. It has a much larger sampling area(27 cm^(2)) and as a result lower method quantification limits(0.15 –0.21 ng/L for one-day deployment and 0.02 – 0.03 ng/L for one-week deployment) and much higher(by > 10 factors) sampling rate(100 m L/day) compared to the standard DGT(piston configuration). The sampler could linearly accumulate PFAS from wastewater, was sensitive enough even for a 24 hr deployment with performance comparable to grab sampling(500m L). The DGT probe provided homogeneous sampling performance along the large exposure area. The use of the probe to investigate distributions of dissolved PFAS around the sediment-water interface was demonstrated. This work, for the first time, demonstrated that the DGT probe is a promising monitoring tool for trace levels of PFAS and a research tool for studying their distribution, migration, and fate in aquatic environments including the sediment-water interface.

Effect of soil pH on the sorption capacity of soil organic matter for polycyclic aromatic hydrocarbons in unsaturated soils

Sorption by soil organic matter(SOM)is considered the most important process affecting the bioavailability of hydrophobic organic chemicals(HOCs)in soil.The sorption capacity of SOM for HOCs is affected by many environmental factors.In this study,we investigated the effects of soil pH and water saturation level on HOC sorption capacity of SOM using batch sorption experiments.Values of soil organic carbon-water partition coefficient(K_(OC))of six selected polycyclic aromatic hydrocarbons(PAHs)were measured in an artificial soil under various soil pH and water saturation conditions.Passive sampling was used to measure K_(OC)with polydimethylsiloxane as the sampling material.Regardless of soil pH,K_(OC)increased with increasing soil water saturation level for lower-molecular-weight PAHs.In contrast,K_(OC)decreased with increasing soil water saturation level for higher-molecular-weight PAHs.Despite some fluctuations,K_(OC)tended to decrease with increasing soil pH at all water saturation levels.This indicates that earlier studies on the effects of soil pH on K_(OC)under saturated conditions could be extended to unsaturated soils.These K_(OC)tendencies were reproduced in three different natural soils,suggesting that the effects of soil water saturation level and pH might be generalized,at least for PAHs.The PAH sorption capacity of SOM was found to be resilient under dynamic soil pH conditions,which can be used to adjust the effects of soil pH.

A review on analytical methods for pharmaceutical and personal care products and their transformation products

Pharmaceutical and personal care products(PPCPs)and corresponding transformation products have caused widespread concern due to their persistent emissions and potential toxicity.They have wide octanol-water partition coefficients(K_(ow))and different ionization constants(pK_(a))resulting in a poor analysis accuracy and efficiency.A suitable analytical method is the first prerequisite for further research on their environmental behavior to prioritize the substances.This study reviewed a full-scale analytical protocol for environmental samples in the recent ten years:from sampling to instrumental methods.Passive sampling techniques were compared and recommended for long-term continuous and scientific observation.A quick and effective sample extraction and clean-up method are highly required.Chromatographic methods coupled to mass spectrometry for determining PPCPs with a wide range of logK_(ow)(-7.53 to 10.80)were summed up.High-resolution mass spectrometry was confirmed to be a promising strategy for screening unknown transformation products,which would provide a nanogram level of detection limits and more accurate mass resolution.Screening strategies and mass change principles were summarized in detail.The recovery rate was important in multiple contaminants analysis identification and factors affecting the recovery rate of PPCPs were also discussed in this review,including sample matrix,target compounds characteristics,extraction method and solid-phase adsorbent.This review provides useful information for the selection of appropriate analytical methods and future development directions.

Sources, distribution, and risk assessment of organochlorine pesticides in Nairobi City, Kenya

The distribution and sources of organochlorine pesticides (OCPs) in air and surface waters were monitored in Nairobi City using triolein-filled semipermeable membrane devices (SP-MDs).The SPMDs were extracted by dialysis using n-hexane,followed by cleanup by adsorption chromatography on silica gel cartridges.Sample analysis was done by GC-ECD and confirmed by GC–MS.Separation of means was achieved by analysis of variance,followed by pair-wise comparison using the t-test (p≤0.05).The total OCPs ranged between 0.018–1.277 ng/m^3 in the air andKibera>Industrial Area>City Square>Ngong’Forest.However,these were lower than the USEPA acceptable risks,10^(-6)–10^(-4).This study concluded that atmospheric OCPs did not pose significant cancer risks to the residents.

Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters

Urban wastewater is one of main sources for the introduction of antibiotics into the environment.Monitoring the concentrations of antibiotics in wastewater is necessary for estimating the amount of antibiotics discharged into the environment through urban wastewater treatment systems.In this study,we report a novel diffusive gradient in thin films(DGT)method based on molecularly imprinted polymers(MIPs)for in situ measurement of two typical antibiotics,fluoroquinolones(FQs)and sulfonamides(SAs)in urban wastewater.MIPs show specific adsorption toward their templates and their structural analogs,resulting in the selective uptake of the two target antibiotics during MIP-DGT deployment.The uptake performance of the MIP-DGTs was evaluated in the laboratory and was relatively independent of solution pH(4.0-9.0),ionic strength(1-750 mmol/L),and dissolved organic matter(DOM,0-20 mg/L).MIP-DGT samplers were tested in the effluent of an urban wastewater treatment plant for field trials,where three SA(sulfamethoxazole,sulfapyridine,and trimethoprim)and one FQ(ofloxacin)antibiotics were detected,with concentrations ranging from 25.50 to 117.58 ng/L,which are consistent with the results measured by grab sampling.The total removal efficiency of the antibiotics was 80.1%by the treatment plant.This study demonstrates that MIP-DGT is an effective tool for in situ monitoring of trace antibiotics in complex urban wastewaters.