A new configuration of polar organic chemical integrative sampler with nylon membranes to monitor emerging organophosphate ester contaminants in urban surface water.

Organophosphate ester contaminants, including organophosphate pesticides (OPPs) and organophosphate flame retardants (OPFRs) are ubiquitous in surface water and pose a significant risk to aquatic organisms, thus it is important to develop effective methods for long-term monitoring of these emerging compounds. Polar organic chemical integrative sampler (POCIS) has become a promising monitoring tool for waterborne contaminants, yet recent studies found that the commonly used polyethersulfone (PES) membrane strongly sorbed some moderately hydrophobic compounds, resulting in long lag-phase for chemical accumulation in POCIS. In the present study, 0.45-µm nylon membranes was selected as POCIS diffusion-limiting membrane to design a new POCIS-Nylon configuration for analyzing moderately hydrophobic OPPs and OPFRs in water. The POCIS-Nylon had negligible lag-phase due to low sorption of OPPs and OPFRs to nylon membrane. Meanwhile, linear accumulation time and sensitivity for target contaminants using POCIS-Nylon retained similar to the traditional POCIS. Water velocity and chemical concentration had little impact on sampling rate (Rs), validating that the POCIS-Nylon was suitable for various water conditions. Finally, the occurrence of OPPs and OPFRs in urban waterways of Guangzhou, China was evaluated using the POCIS-Nylon with Rs values that were calibrated in the laboratory. The average concentration of OPPs was 4.97 ± 1.35 ng/L (range: 2.64 ± 1.28-6.54 ± 0.18 ng/L) and the average concentration of OPFRs was 400 ± 88 ng/L (range: 316 ± 24-615 ± 36 ng/L) across nine sampling sites. The present study provides a way to resolve the inherent challenge of accumulating hydrophobic substances by POCIS.

Bioaccumulation of highly hydrophobic organohalogen flame retardants from sediments: application of toxicokinetics and passive sampling techniques.

Highly hydrophobic organohalogen flame retardants (HHOFRs) are found ubiquitously in the environment; therefore, a better understanding of their bioavailability is needed. In the current study, bioaccumulation testing using the oligochaete, Lumbriculus variegatus, and passive sampling (solid-phase microextraction (SPME)) were performed to study the bioaccumulation potential of HHOFRs, including decabromodiphenyl ether (deca-BDE), decabromodiphenyl ethane (DBDPE), and dechlorane plus (DP), in laboratory-spiked and field-collected sediments. The HHOFRs were bioavailable to L. variegatus even though their biota-sediment accumulation factors were low (0.016 ± 0.002 to 0.48 ± 0.082 g organic carbon/g lipid, syn-DP > anti-DP > deca-BDE > DBDPE). Hydrophobicity and stereoisomerism affected HHOFR bioavailability. Meanwhile, HHOFR concentrations on the SPME fibers (Cf) correlated with those in biota (Cb), suggesting the potential application of SPME in bioavailability prediction for those compounds. The log Cf to log Cb correlation for deca-BDE and DP had a greater intercept than that for polychlorinated biphenyls (data obtained from the literature) although the slopes were similar, while data for DBDPE fell on the regression line for PCBs, implying some uncertainty in application of SPMEs across chemical classes. The increasing sorptive ability of proteins for HHOFRs in comparison to the less-brominated BDEs suggested that protein-binding should be considered when estimating bioaccumulation potential of HHOFRs in benthic invertebrates.

Determining buffering capacity of polydimethylsiloxane-based passive dosing for hydrophobic organic compounds in large-volume bioassays.

Polydimethylsiloxane (PDMS) is the most widely used material for passive dosing. However, the ability of PDMS to maintain constant water concentrations of chemicals in large-volume bioassays was insufficiently investigated. In this study, we proposed a kinetic-based method to determine the buffering capacity of PDMS for maintaining constant water concentrations of hydrophobic organic contaminants (HOCs) in large-volume bioassays. A good correlation between log Kow and PDMS-water partitioning coefficients (log KPW) was observed for HOCs with log Kow values ranging from 3.30 to 7.42. For low-molecular-weight HOCs, volatile loss was identified as the primary cause of unstable water concentrations in passive dosing systems. Slow desorption from PDMS resulted in a reduction of water concentrations for high-molecular-weight HOCs. The volume ratio of PDMS to water (RV) was the key factor controlling buffering capacity. As such, buffering capacity was defined as the minimum RV required to maintain 90% of the initial water concentration and was determined to be 0.0076-0.032 for six representative HOCs. Finally, passive dosing with an RV of 0.014 was validated to effectively maintain water concentrations of phenanthrene in 2-L and 96-h toxicity tests with adult mosquitofish. By determining buffering capacity of PDMS, this study recommended specific RV values for cost-efficient implementation of passive dosing approaches in aquatic toxicology, particularly in large-volume bioassays.

Bioavailability of hydrophobic organic contaminants in sediment with different particle-size distributions.

Few studies have been conducted examining the distribution of different-sized particles in sediment and its potential impact on bioavailability of sediment-associated contaminants. In the current study, three sediments composed of different particle sizes, i.e., fine (0-180 µm), combined (0-500 µm), and coarse (180-500 µm), were used to evaluate the bioaccumulation potential and toxicokinetic rates of four hydrophobic organic contaminants (HOCs) including two polychlorinated biphenyls (PCB-101 and PCB-118), a metabolite of an organochlorine insecticide (p,p'-DDE), and a polybrominated diphenyl ether (BDE-47) to the benthic oligochaete Lumbriculus variegatus. Two chemical approaches, Tenax extraction and matrix-solid phase microextraction (SPME), were also used to measure bioavailability of the sediment-associated HOCs. The uptake and elimination rates of HOCs by L. variegatus from coarse sediment were greater than those from fine sediment, although the biota-sediment accumulation factors (BSAFs) were not significantly different among sediments with different particle sizes. The freely dissolved HOC concentrations measured by matrix-SPME were greater in coarse sediment, however, no difference was found in uptake and desorption rates for the matrix-SPME and Tenax extraction measurements. Although BSAFs in L. variegatus were the same among sediments, kinetic rates of HOCs for organisms and freely dissolved HOC concentrations were lower in fine sediment, suggesting that sediment ingestion may also play a role in organism uptake, especially for HOCs in fine sediment.

Measuring bioconcentration factors of sediment-associated fipronil in Lumbriculus variegatus using passive sampling techniques.

Fipronil and its degradates have been detected ubiquitously in aquatic environment worldwide, yet little is known about its bioaccumulation potential. The goal of the present study was to measure bioconcentration factor (BCF) of sediment-associated fipronil in a benthic invertebrate, Lumbriculus variegatus using passive sampling techniques. Three passive samplers including polymethyl methacrylate (PMMA) film, poly(dimethylsiloxane) fiber and polyacrylate fiber were evaluated. PMMA film was identified as the preferred method and was applied to determine fipronil log KOC (3.77 ±â€¯0.04). BCF of sediment-associated fipronil in L. variegatus was obtained through measuring freely dissolved concentration (Cfree). Because fipronil degraded in sediment, time weighted average (TWA) Cfree was estimated for calculating BCFTWA (1855 ±â€¯293 mL/g lipid). Fipronil BCF was also measured in a water-only bioaccumulation test of L. variegatus under constant exposure condition. This BCF value (1892 ±â€¯76 mL/g lipid) was comparable with the BCFTWA, validating effectiveness of the passive sampling method for the measurement of sediment Cfree. Fipronil was bioaccumulative in L. variegatus according to the USEPA's criteria. The combination of Cfree and TWA concentration measurements was demonstrated to properly determine BCF value for moderately hydrophobic and degradable chemicals in sediment.

Determining equilibrium partition coefficients between lipid/protein and polydimethylsiloxane for highly hydrophobic organic contaminants using preloaded disks.

Bioaccumulation of hydrophobic organic contaminants is of great concern and understanding their partitioning to biological phases is crucial for estimating their bioaccumulation potential. The estimation, however, was of large uncertainty for highly hydrophobic organic contaminants (HHOCs) with log KOW>9 due to the challenge of quantifying their water concentrations. In the present study, partition coefficients between polydimethylsiloxane (PDMS) and storage lipid (KSL,PDMS), membrane lipid (KML,PDMS) and protein (Kpro,PDMS) were measured for 21 polychlorinated biphenyls (PCBs), 14 polybrominated diphenyl ethers (PBDEs), dechlorane plus (DP) and decabromodiphenyl ethane (DBDPE), covering log KOW from 5.07 to 11.6, using a preloaded PDMS depletion method. The values of KSL,PDMS, KML,PDMS and Kpro,PDMS were in the ranges of 5.36-52.5, 0.286-11.8 and 0.067-2.62g/g, respectively, being relatively constant although their KOW values extend more than six orders of magnitude. The relative sorption capacity of the biological phases showed storage lipid was the dominant sorption phase in biota, followed by membrane lipid and protein was the lowest. The KPDMS,pro values of the compounds with log KOW<9 were similar (0.382-14.9g/g) regardless of the thickness of preloaded PDMS disks (58-209µm). For HHOCs, however, KPDMS,pro values dropped when thinner PDMS disks were used, as a result of slow diffusion of HHOCs in PDMS. The KPDMS,pro values of HHOCs measured by 58-µm PDMS disks ranged from 1.78 to 6.85g/g, which was consistent with compounds with log KOW<9. This validated that partition coefficients between PDMS and biological phases were independent of chemical hydrophobicity, showing the advantage of using PDMS-based methods to directly estimate bioaccumulation potential of HHOCs.

[Investigation on the association of safety perception and safety behaviors with occupational injuries in steel-workers].

OBJECTIVE: To explore the association of occupational injuries, with their individual safety perception and safety behaviors in steel workers, so as to provide basis for preventing and controlling occupational injuries. METHODS: Case-control design was used to compare the difference in safety perception and safety behaviors between the injury group and the control, and also to compare the difference in safety behaviors between different safety perception groups. RESULTS: There were remarkable differences in attitude toward the safety degree of the work (chi(2) = 5.444, P < 0.05), and accidents happening (chi(2) = 4.552, P < 0.05) between case group and control group. There were remarkable difference in safety behaviors including manual operations instead of facilities (chi(2) = 10.015, P < 0.01), cleaning up, examining or adjusting machine during work (chi(2) = 7.351, P < 0.05), attention diversion (chi(2) = 10.937, P < 0.01) and unsafe wearing (chi(2) = 7.521, P < 0.05) between case group and control group. There were also significant differences in many safety behaviors between those who thought the job was safe or unsafe. CONCLUSION: There is some association of occupational injuries with safety perception and safety behaviors. To reduce the occurrence of occupational injury, measures should been focused on strengthening safety management and controlling unsafe behaviors.