Passive-Sampler-Derived PCB and OCP Concentrations in the Waters of the World─First Results from the AQUA-GAPS/MONET Network.

Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.

Field Evaluation and in Situ Stress Testing of the Organic-Diffusive Gradients in Thin-Films Passive Sampler.

The organic-diffusive gradients in thin-films (o-DGT) technique has emerged as a promising aquatic passive sampler that addresses many of the challenges associated with current sampling tools used for measurement of polar organic contaminants. This study represents the first comprehensive field evaluation of the o-DGT in natural surface waters, across a wide suite of polar pharmaceuticals and pesticides. We explore the utility and limitations of o-DGT as a quantitative measurement tool compared to grab sampling and the polar organic chemical integrative sampler (POCIS) across four connected agricultural and wastewater-influenced freshwater systems spanning 600 km from the U.S. border to northern Manitoba, Canada. Overall, the suite of analytes detected with o-DGT and POCIS was similar. Concentrations in water estimated using o-DGT were greater than concentrations estimated from POCIS in 71 of 80 paired observations, and on average, the estimates from o-DGT were 2.3-fold greater than estimates from POCIS. Grab sample concentrations suggested that the systematic underestimation with POCIS were largely a result of sampling rate variation related to flow rate and boundary-layer effects, an issue reported consistently in the POCIS literature. These comprehensive measurements in an agriculturally influenced fast-flowing river, long-term sampling (>40 days) in a large dilute lake system, deployments in wastewaters, and under ice at near-freezing temperatures represent effective stress testing of o-DGT under representative and challenging conditions. Overall, its strong performance and improved accuracy over POCIS supports its use as a robust, quantitative, and sensitive measurement tool for polar organic chemicals in aquatic systems.

Aquatic Global Passive Sampling (AQUA-GAPS) Revisited: First Steps toward a Network of Networks for Monitoring Organic Contaminants in the Aquatic Environment.

Organic contaminants, in particular persistent organic pollutants (POPs), adversely affect water quality and aquatic food webs across the globe. As of now, there is no globally consistent information available on concentrations of dissolved POPs in water bodies. The advance of passive sampling techniques has made it possible to establish a global monitoring program for these compounds in the waters of the world, which we call the Aquatic Global Passive Sampling (AQUA-GAPS) network. A recent expert meeting discussed the background, motivations, and strategic approaches of AQUA-GAPS, and its implementation as a network of networks for monitoring organic contaminants (e.g., POPs and others contaminants of concern). Initially, AQUA-GAPS will demonstrate its operating principle via two proof-of-concept studies focused on the detection of legacy and emerging POPs in freshwater and coastal marine sites using both polyethylene and silicone passive samplers. AQUA-GAPS is set up as a decentralized network, which is open to other participants from around the world to participate in deployments and to initiate new studies. In particular, participants are sought to initiate deployments and studies investigating the presence of legacy and emerging POPs in Africa, Central, and South America.

Development and Calibration of an Organic-Diffusive Gradients in Thin Films Aquatic Passive Sampler for a Diverse Suite of Polar Organic Contaminants.

A unique configuration of the diffusive gradients in thin films sampler for polar organics (o-DGT) without a poly(ether sulfone) membrane was developed, calibrated, and field-evaluated. Diffusion coefficients (D) through agarose diffusive gels ranged from (1.02 to 4.74) × 10-6 cm2/s for 34 pharmaceuticals and pesticides at 5, 13, and 23 °C. Analyte-specific diffusion-temperature plots produced linear (r2 > 0.85) empirical relationships whereby D could be estimated at any environmentally relevant temperature (i.e., matched to in situ water conditions). Linear uptake for all analytes was observed in a static renewal calibration experiment over 25 days except for three macrolide antibiotics, which reached saturation at 300 ng (≈15 d). Experimental sampling rates ranged from 8.8 to 16.1 mL/d and were successfully estimated with measured and modeled D within 19% and 30% average relative error, respectively. Under slow flowing (2.4 cm/s) and static conditions, the in situ diffusive boundary layer (DBL) thickness ranged from 0.023 to 0.075 cm, resulting in a maximum contribution to mass transfer of <45%. Estimated water concentrations by o-DGT at a wastewater treatment plant agreed well with grab samples and appeared to be less influenced by the boundary layer compared to that of polar organic chemical integrative samplers (POCIS) deployed simultaneously. The o-DGT sampler is a promising monitoring tool that is largely insensitive to the DBL under typical flow conditions, facilitating the application of measured/modeled diffusion-based sampling rates. This significantly reduces the need for sampler calibration, making o-DGT more widely applicable, reliable, and cost-effective compared to current polar passive samplers.

Chronic exposure to perfluorinated compounds: Impact on airway hyperresponsiveness and inflammation.

Emerging epidemiological evidence reveals a link between lung disease and exposure to indoor pollutants such as perfluorinated compounds (PFCs). PFC exposure during critical developmental stages may increase asthma susceptibility. Thus, in a murine model, we tested the hypothesis that early life and continued exposure to two ubiquitous household PFCs, perfluorooctanoic acid (PFOA) and perflurooctanesulfonic acid (PFOS), can induce lung dysfunction that exacerbates allergen-induced airway hyperresponsiveness (AHR) and inflammation. Balb/c mice were exposed to PFOA or PFOS (4 mg/kg chow) from gestation day 2 to 12 wk of age by feeding pregnant and nursing dams, and weaned pups. Some pups were also sensitized and challenged with ovalbumin (OVA). We assessed lung function and inflammatory cell and cytokine expression in the lung and examined bronchial goblet cell number. PFOA, but not PFOS, without the OVA sensitization/challenge induced AHR concomitant with a 25-fold increase of lung macrophages. PFOA exposure did not affect OVA-induced lung inflammatory cell number. In contrast, PFOS exposure inhibited OVA-induced lung inflammation, decreasing total cell number in lung lavage by 68.7%. Interferon-γ mRNA in the lung was elevated in all PFC-exposed groups. Despite these effects, neither PFOA nor PFOS affected OVA-induced AHR. Our data do not reveal PFOA or PFOS exposure as a risk factor for more severe allergic asthma-like symptoms, but PFOA alone can induce airway inflammation and alter airway function.

Development of an accreditation process for analytical methods to measure microplastics in drinking water for regulatory monitoring.

Development of a laboratory accreditation program to ensure competency of laboratories performing analytical measurements is a key step in adopting new analytical measurement methods for regulatory decision-making. Here, we describe California's three-part accreditation process for spectroscopically measuring microplastics in drinking water, and show how data from a multi-laboratory method comparison study informed development of accreditation programs for the resulting methods, which can inform analogous future work for other analytes. The first part is periodic performance evaluation (PE) samples, in which laboratories are provided blind samples of known composition to quantify within acceptable performance limits. The second is inspection, or audit, assessing whether the laboratory has the proper equipment to conduct the work and whether it is correctly employing proper procedures. The third is implementation of a quality management system providing documentation that protocols demonstrated during inspection are continuously maintained. These fell into three broad categories: instrument maintenance; laboratory cleanliness, especially important for microplastics and one that must be accompanied by a blanks measurement and correction process; and training so samples are being processed by qualified analysts. An intercomparison exercise among 22 laboratories was necessary to determine what parameter permutations were important for PE samples, and expected accuracy from competent laboratories. The recommended PE sample composition was two size categories (20-50um and 500um-1mm), two polymer types, and two morphologies (fibers and non-fibers). Discussions among intercomparison exercise participants were key in determining the factors that most contributed to laboratory variability, and the focus for both on-site inspections and quality management systems.

Development and validation of an acid/alkaline digestion method for efficient microplastic extraction from wastewater treatment plant effluents: Sulfuric acid concentration and contact time do matter.

Accurate analysis of microplastic particles (MPs) in environmental samples requires removal of interferences during sample preparation. Wastewater samples are interference-rich and thus particularly challenging, with concentrated sulfuric acid currently deemed impractical as a reagent. Therefore, this study aimed to establish a straightforward, effective, and safe method employing concentrated sulfuric acid and potassium hydroxide to eliminate interferents from effluent samples obtained from wastewater treatment plants (WWTPs). We found that 80 % sulfuric acid at room temperature with a brief contact time of 5 min was viable through a qualitative spot test involving 37 plastics categorized into three types (I, II, and III) based on their polymer structure's oxygen position. A quantitative assessment revealed that treatments involving H2SO4 and KOH (20 %, 24 h, 48 °C), either separately or in combination, had no discernible physical impact on the overall plastics, except for a subtle one for Type III plastics (e.g., nylon and PMMA) known to be labile under harsh pH conditions. This acid/alkaline digestion (AAD) method, incorporating such conditions for H2SO4 and KOH treatments, yielded a high mass removal efficacy (97.8 ± 2.4 %, n = 13) for eliminating natural particle interferents for primary, secondary, and tertiary effluent samples. Furthermore, the AAD method allowed for the determination of MPs in effluents with high surrogate particle recoveries (e.g., 95.1 % for larger than 500 µm size fraction). This method is readily adaptable to create appropriate protocols for different types of environmental matrices.

Utility of a modified o-DGT passive sampler for measurement of bisphenol analogues in freshwater and coastal waters.

Bisphenol analogues (BPs) are commonly found in riverine and coastal waters. However, the lack of a reliable and robust passive sampling method has hindered our ability to monitor these compounds in aquatic systems. The study developed a novel organic-diffusive gradients in thin film (o-DGT) sampler based on stainless steel mesh membrane, polyacrylamide diffusive gel, and hydrophilic-lipophilic balance (HLB) binding gel. This innovative design tackled issues of filter membrane sorption in traditional o-DGT devices and potential gel damage in membrane-less o-DGT devices, showing promising application prospects. The mass accumulation of 15 target BPs was linear over 10 days in both freshwater (r2 ≥ 0.92) and seawater (r2 ≥ 0.94), with no saturation observed. The diffusion coefficients (D) through polyacrylamide diffusive gels ranged from 4.04 × 10-6 to 5.77 × 10-6 cm2 s-1 in freshwater and from 1.74 × 10-6 to 4.69 × 10-6 cm2 s-1 in seawater for the target BPs (except for bisphenol PH) at 22 °C. The D values of the target BPs in seawater were lower than those in freshwater due to the high salinity in seawater (35 ‰). The o-DGT samplers demonstrated good integrity in field applications. The total concentrations of the eight detected BPs ranged from 9.2 to 323 ng L-1, which was consistent with the measurements obtained by grab sampling. Among all BPs, bisphenol S, bisphenol F, and bisphenol A were consistently detected at all sites using both sampling methods. The concentrations of some novel BPs in coastal water measured by grab sampling were comparable to those measured in rivers, suggesting the need to strengthen pollution control of BPs in coastal areas. These results indicate that the o-DGT passive sampling method developed in the present study can be effectively used for monitoring BPs in freshwater and coastal environments.

Stereoselective formation of mono- and dihydroxylated polychlorinated biphenyls by rat cytochrome P450 2B1.

Changes in atropisomer composition of chiral polychlorinated biphenyls (PCBs) and their mono- and dihydroxylated metabolites (OH- and diOH-PCBs) via rat cytochrome P450 2B1 (CYP2B1) mediated biotransformation were investigated in vitro. Rat CYP2B1 could stereoselectively biotransform chiral PCBs to generate meta-OH-PCBs as the major metabolites after 60 min incubations. Nonracemic enantiomer fractions (EFs: concentration ratios of the (+)-atropisomer or the first-eluting atropisomer over the total concentrations of two atropisomers) of 5-OH-PCBs, were 0.17, 0.20, 0.85, 0.77, and 0.41 for incubations with PCBs 91, 95, 132, 136, and 149, respectively. CYP-mediated stereoselective formation of diOH-PCBs from OH-PCBs was observed for the first time. After 60 min stereoselective biotransformation, the EFs of both 4-OH-PCB 95 and 5-OH-PCB 95 changed from racemic (i.e., 0.50) to 0.62 and 0.46, respectively. These transformations generated statistically nonracemic 4,5-diOH-PCB 95, with EFs of 0.53 and 0.58 for 4-OH-PCB 95 and 5-OH-PCB 95 incubations, respectively. Biotransformation of PCBs 91 and 136 also generated 4,5-diOH-PCB 91 and 4,5-diOH-PCB 136, respectively. These in vitro results were consistent with that observed for stereoselective PCB biotransformation by rat liver microsomes and in vivo. Biotransformation interference between two atropisomers of PCB 136 was investigated for the first time in this study. The biotransformation process of (-)-PCB 136 was significantly disrupted by the presence of (+)-PCB 136 but not the other way around. Thus, stereoselective metabolism of chiral PCBs and OH-PCBs by CYPs is a major mechanism for atropisomer composition change of PCBs and their metabolites in the environment, with the degree of composition change dependent, at least in part, on stereoselective interference of atropisomers with each other at the enzyme level.

Anthropogenic activities have contributed moderately to increased inputs of organic materials in marginal seas off China.

Sediment has been recognized as a gigantic sink of organic materials and therefore can record temporal input trends. To examine the impact of anthropogenic activities on the marginal seas off China, sediment cores were collected from the Yellow Sea, the inner shelf of the East China Sea (ECS), and the South China Sea (SCS) to investigate the sources and spatial and temporal variations of organic materials, i.e., total organic carbon (TOC) and aliphatic hydrocarbons. The concentration ranges of TOC were 0.5-1.29, 0.63-0.83, and 0.33-0.85%, while those of Σn-C14-35 (sum of n-alkanes with carbon numbers of 14-35) were 0.08-1.5, 0.13-1.97, and 0.35-0.96 µg/g dry weight in sediment cores from the Yellow Sea, ECS inner shelf, and the SCS, respectively. Terrestrial higher plants were an important source of aliphatic hydrocarbons in marine sediments off China. The spatial distribution of Σn-C14-35 concentrations and source diagnostic ratios suggested a greater load of terrestrial organic materials in the Yellow Sea than in the ECS and SCS. Temporally, TOC and Σn-C14-35 concentrations increased with time and peaked at either the surface or immediate subsurface layers. This increase was probably reflective of elevated inputs of organic materials to marginal seas off China in recent years, and attributed partly to the impacts of intensified anthropogenic activities in mainland China. Source diagnostics also suggested that aliphatic hydrocarbons were mainly derived from biogenic sources, with a minority in surface sediment layers from petroleum sources, consistent with the above-mentioned postulation.

How to establish detection limits for environmental microplastics analysis.

Establishing analytical detection limits is crucial. Common methods to do so are suitable only for variables with continuous distributions. Because count data for microplastic particles is a discrete variable following the Poisson distribution, currently-used approaches for estimating the detection limit in microplastics analysis are inadequate. Here we evaluate detection limits with techniques for low-level discrete observations to develop proper approaches for estimating the minimum detectable amount (MDA) in microplastic particle analysis, using blank sample data from an interlaboratory calibration exercise for clean water (representing drinking water), dirty water (ambient water), sediment (porous media) and fish tissue (biotic tissues). Two MDAs are applicable: MDAA to evaluate analytical methods, estimated with replicate blank data; and MDAB for individual sample batches, calculated with a single blank count. For illustrative purposes, this dataset's overall MDAA values were 164 counts (clean water), 88 (dirty water), 192 (sediment), and 379 (tissue). MDA values should be reported on a laboratory-specific basis and for individual size fractions, as this provides more useful information about capabilities of individual laboratories. This is due to wide variation in blank levels, as noted by MDAB values (i.e., among different laboratories) from 14 to 158 (clean water), 9 to 86 (dirty water, 9 to 186 (sediment), and 9 to 247 (tissue). MDA values for fibers were considerably greater than for non-fibers, suggesting that separate MDA values should be reported. This study provides a guideline for estimation and application of microplastics MDA for more robust data to support research activities and environmental management decisions.

Comparison of two procedures for microplastics analysis in sediments based on an interlaboratory exercise.

Microplastics (MP) are distributed throughout ecosystems and settle into sediments where they may threaten benthic communities; however, methods for quantifying MP in sediments have not been standardized. This study compares two methods for analyzing MP in sediments, including extraction and identification, and provides recommendations for improvement. Two laboratories processed sediment samples using two methods, referred to as "core" and "augmentation", and identified particles with visual microscopy and spectroscopy. Using visual microscopy, the augmentation method yielded mean recoveries (78%) significantly greater than the core (47%) (p = 0.03), likely due to the use of separatory funnels in the former. Spectroscopic recovery of particles was lower at 42 and 54% for the core and augmentation methods, respectively. We suspect the visual identification recoveries are overestimations from erroneous identification of non-plastic materials persisting post-extraction, indicating visual identification alone is not an accurate method to identify MP, particularly in complex matrices like sediment. However, both Raman and FTIR proved highly accurate at identifying recovered MP, with 96.7% and 99.8% accuracy, respectively. Low spectroscopic recovery of spiked particles indicates that MP recovery from sediments is lower than previously assumed, and MP may be more abundant in sediments than current analyses suggest. To our knowledge, likely due to the excessive time/labor-intensity associated with MP analyses, this is the first interlaboratory study to quantify complete method performance (extraction, identification) for sediments, with regards to capabilities and limitations. This is essential as regulatory bodies move toward long-term environmental MP monitoring.

Patterns of microparticles in blank samples: A study to inform best practices for microplastic analysis.

Quality assurance and quality control (QA/QC) techniques are critical to analytical chemistry, and thus the analysis of microplastics. Procedural blanks are a key component of QA/QC for quantifying and characterizing background contamination. Although procedural blanks are becoming increasingly common in microplastics research, how researchers acquire a blank and report and/or use blank contamination data varies. Here, we use the results of laboratory procedural blanks from a method evaluation study to inform QA/QC procedures for microplastics quantification and characterization. Suspected microplastic contamination in the procedural blanks, collected by 12 participating laboratories, had between 7 and 511 particles, with a mean of 80 particles per sample (±SD 134). The most common color and morphology reported were black fibers, and the most common size fraction reported was 20-212 µm. The lack of even smaller particles is likely due to limits of detection versus lack of contamination, as very few labs reported particles <20 µm. Participating labs used a range of QA/QC techniques, including air filtration, filtered water, and working in contained/'enclosed' environments. Our analyses showed that these procedures did not significantly affect blank contamination. To inform blank subtraction, several subtraction methods were tested. No clear pattern based on total recovery was observed. Despite our results, we recommend commonly accepted procedures such as thorough training and cleaning procedures, air filtration, filtered water (e.g., MilliQ, deionized or reverse osmosis), non-synthetic clothing policies and 'enclosed' air flow systems (e.g., clean cabinet). We also recommend blank subtracting by a combination of particle characteristics (color, morphology and size fraction), as it likely provides final microplastic particle characteristics that are most representative of the sample. Further work should be done to assess other QA/QC parameters, such as the use of other types of blanks (e.g., field blanks, matrix blanks) and limits of detection and quantification.

The influence of complex matrices on method performance in extracting and monitoring for microplastics.

Previous studies have evaluated method performance for quantifying and characterizing microplastics in clean water, but little is known about the efficacy of procedures used to extract microplastics from complex matrices. Here we provided 15 laboratories with samples representing four matrices (i.e., drinking water, fish tissue, sediment, and surface water) each spiked with a known number of microplastic particles spanning a variety of polymers, morphologies, colors, and sizes. Percent recovery (i.e., accuracy) in complex matrices was particle size dependent, with ∼60-70% recovery for particles >212 µm, but as little as 2% recovery for particles <20 µm. Extraction from sediment was most problematic, with recoveries reduced by at least one-third relative to drinking water. Though accuracy was low, the extraction procedures had no observed effect on precision or chemical identification using spectroscopy. Extraction procedures greatly increased sample processing times for all matrices with the extraction of sediment, tissue, and surface water taking approximately 16, 9, and 4 times longer than drinking water, respectively. Overall, our findings indicate that increasing accuracy and reducing sample processing times present the greatest opportunities for method improvement rather than particle identification and characterization.

Isomer-specific biotransformation of perfluorooctane sulfonamide in Sprague-Dawley rats.

Great variability exists in perfluorooctane sulfonate (PFOS) isomer patterns in human and wildlife samples, including unexpectedly high percentages (e.g., >40%) of branched isomers in human sera. Previous in vitro tests showed that branched PFOS-precursors were biotransformed faster than the corresponding linear isomer. Thus, high percentages of branched PFOS may be a biomarker of PFOS-precursor exposure in humans. We evaluated this hypothesis by examining the isomer-specific fate of perfluorooctane sulfonamide (PFOSA), a known PFOS-precursor, in male Sprague-Dawley rats exposed to commercial PFOSA via food for 77 days (83.0 ± 20.4 ng kg(-1) day(-1)), followed by 27 days of depuration. Elimination half-lives of the two major branched PFOSA isomers (2.5 ± 1.0 days and 3.7 ± 1.2 days) were quicker than for linear PFOSA (5.9 ± 4.6 days), resulting in a depletion of branched PFOSA isomers in blood and tissues relative to the dose. A corresponding increase in the total branched isomer content of PFOS, the ultimate metabolite, in rat serum was not observed. However, a significant enrichment of 5m-PFOS and a significant depletion of 1m-PFOS were observed, relative to authentic electrochemical PFOS. The data cannot be directly extrapolated to humans, due to known differences in the toxicokinetics of PFOS in rodents and humans. However, the results confirm that in vivo exposure to commercially relevant PFOS-precursors can result in a distinct PFOS isomer profile that may be useful as a biomarker of exposure source.

Size-dependent dry deposition of airborne polybrominated diphenyl ethers in urban Guangzhou, China.

Gaseous and size-segregated particulate PBDEs (specifically BDE-47, -99, -183, -207, and -209) in the air were measured in urban Guangzhou at 100 and 150 m above the ground in daytime and at night in August and December 2010, to assess dry deposition of these contaminants accurately with regards to influences of meteorological factors but without confounding surface effects. Particulate PBDEs were more abundant at night than in daytime, and slightly higher in winter than in summer, likely from varying meteorological conditions and atmospheric boundary layers. More than 60% of particulate-phase PBDEs was contained in particles with an aerodynamic diameter (D(p)) below 1.8 µm, indicating long-range transport potential. The average daily particle dry deposition fluxes of PBDEs in August ranged from 2.6 (BDE-47) to 88.6 (BDE-209) ng m(-2) d(-1), while those in winter ranged from 2.0 (BDE-47) to 122 (BDE-209) ng m(-2) d(-1). Deposition fluxes of all PBDE congeners were significantly higher in daytime than at night for both months, due to the effect of diurnal variability of meteorological factors. In addition, mean overall particle deposition velocities of individual BDE congeners ranged from 0.11 to 0.28 cm s(-1). These values were within a factor of 2 of assumed values previously used in southern China and the Laurentian Great Lakes, suggesting that such assumptions were reasonable for sites with similar particulate size distributions and PBDE sources. Dry deposition velocities of PBDEs were lower at night than those in the daytime, probably reflecting higher mechanical and thermal turbulence during daytime. Dry deposition of particulate-bound PBDEs is influenced by short-term temporal variability from meteorological factors, and also by particulate size fractions.

Sediment records of polycyclic aromatic hydrocarbons (PAHs) in the continental shelf of China: implications for evolving anthropogenic impacts.

Sources, compositions, and historical records of polycyclic aromatic hydrocarbons (PAHs) in sediment cores collected from the Yellow Sea and the South China Sea were analyzed to investigate the influence of anthropogenic activities. The occurrence of PAHs was mainly derived from various combustion sources, especially the combustion of biomass and domestic coal. Uniform composition of sedimentary PAHs (52-62% of phenanthrene, benzo[b]fluoranthene, indeno[1,2,3-cd]pyrene, and benzo[g,h,i]perylene) suggested air-borne mixtures intractable to degradation. The concentrations of the sum of 15 PAHs (16 priority pollutants designed by the United States Environmental Protection Agency minus naphthalene; designed as Σ(15)PAH) in Yellow Sea sediment cores were generally higher than those in the South China Sea. The profiles of Σ(15)PAH concentrations recorded in the sediment cores closely followed historical socioeconomic development in China. In general, Σ(15)PAH concentrations started to increase from the background pollution level posed by agricultural economy at the turn of 20th century. In addition, a Σ(15)PAH concentration reduction was observed during the Chinese Civil War (1946-1949) and Great Cultural Revolution (1966-1976), suggesting them as setbacks for economic development in Chinese history. Increasing PAH emissions as a result of increasing coal combustion associated with the rapid urbanization and industrialization since the implementation of the Reform and Open Policy (since 1978) accounted for the fast growth of Σ(15)PAH concentrations in sediment cores. The decline of Σ(15)PAH concentrations from subsurface maximum until sampling time was inconsistent with current-day economic development in China, and may possibly suggest emission reductions due to decreasing proportional use of domestic coal and increasing consumption of cleaner energies (natural gas and liquefied petroleum gas).

Enantiospecific perfluorooctane sulfonate (PFOS) analysis reveals evidence for the source contribution of PFOS-precursors to the Lake Ontario foodweb.

Exposure to perfluorooctane sulfonate (PFOS) may arise directly, from emission and exposure to PFOS itself, or indirectly via the environmental release and degradation of PFOS-precursors. Human serum enantiomer fractions (EFs) of 1m-PFOS have been shown to be nonracemic, suggesting that PFOS-precursors are a significant source of PFOS in humans, but little is known about the importance of PFOS-precursors in ecosystems. In the current work, concentrations of PFOS, perfluorooctane sulfonamide (PFOSA), PFOS isomer profiles, and EFs of 1m-PFOS were determined in Lake Ontario water, sediment, fishes and invertebrates. Concentrations of PFOS and PFOSA were highest in slimy sculpin and Diporeia, and concentrations of the two compounds were often correlated. 1m-PFOS was racemic in sediment, water, sculpin and rainbow smelt, but nonracemic in the top predator, lake trout, and all invertebrate species. Furthermore, EFs were correlated with the relative concentrations of PFOS and PFOSA in invertebrates. Overall, these empirical observations with a new analytical tool confirm previous suggestions that PFOS-precursors contribute to PFOS in the food web, likely via sediment. Implications are that future PFOS exposures in this ecosystem will be influenced by an in situ source, and that the apparent environmental behavior of PFOS (e.g., bioaccumulation potential) can be confounded by precursors.

Sedimentary loadings and ecological significance of polycyclic aromatic hydrocarbons in a typical mariculture zone of South China.

Two sediment cores were collected from Hailing Bay located in a typical mariculture zone of Guangdong Province, South China, and analyzed for polycyclic aromatic hydrocarbons (PAHs). The concentrations of the sum of 27 PAHs ranged from 62 to 1200 ng g(-1) dry wt, and sediment in the study area was considered to be moderately polluted by PAHs. Source diagnostics based on PAH composition and principal component analysis suggested that PAHs in the study area were mainly derived from petroleum combustion, with discharge of PAHs from fishing boats as an important source. Ecological risk assessment results indicate that PAHs in sediment of the present study currently have minimal adverse effect on the mariculture environment. Comparison of sedimentary inventory of PAHs in the fish harbor of the study area with those in the Pearl River Estuary and the coastal Bohai Bay indicate that the sediment has become an important reservoir of PAHs.

Scrutinizing surficial sediment along a 600-km-long urban coastal zone: Occurrence and risk assessment of fipronil and its three degradates.

Contamination in the coastal zone is closely linked to urbanization and has become a global issue. The coastal aquatic environment is the terminal sink for many chemicals; however, little is known about the occurrence and variation among habitats as well as integrative toxicity for pesticides, i.e., fipronil, and its three major degradates (-desulfinyl, -sulfide, and -sulfone, fiproles hereafter) in sediments in urban coastlines. In the present study, we report results of a random stratified survey for fiproles in surficial sediments in five embayment habitats (strata) along the Southern California Bight (SCB), USA coastline. Fiproles were present in a small areal extent (6.8%) of the SCB embayment, and detected in 14 out of 174 stations with a total concentration of the four analytes ranging from 0.50 to 17.5 µg/kg dry weight. The area-weighted mean concentrations were 3.16 ± 3.37, 0.584 ± 0.558, 0.071 ± 0.103, and 0.005 ± 0.009 µg/kg in brackish estuaries, estuaries, bays, and marinas, respectively, with the results below the detection limits in ports. Fipronil sulfone had the greatest detection frequency (8.05%) and highest mean concentration (3.24 ± 3.36 µg/kg) among the four compounds. A screening-level deterministic risk assessment for invertebrates found that, region-wide, fiproles generally posed an insignificant to low acute risk to the amphipod Eohaustorius estuarius in 7.36% of the SCB embayment area. In addition, high risk to the midge Chironomus dilutus was found in 77.5% of the fiproles-detectable area in the brackish estuary stratum that is a part of the Los Angeles River. Fipronil sulfone was identified as the major contributor of these effects. The results of this study establish a baseline of occurrence and toxicity potential for fiproles in coastal sediments of southern California.