Organophosphate Esters In Sediment Research Articles

Temporal trends of plastic additive contents in sediment cores of three French rivers (Loire, Meuse and Moselle) over the last decades

Sediment cores from three major French watersheds (Loire, Meuse and Moselle) have been dated by 137Cs and 210Pbxs from 1910 (Loire), 1947 (Meuse) and 1930 (Moselle) until the present in order to reconstruct trajectories of plastic additive contaminants including nine phthalate esters (PAEs) and seven organophosphate esters (OPEs), measured by gas chromatography–mass spectrometer (GC–MS–MS). Historical levels of ∑PAEs were higher than those of ∑OPEs in the Loire and the Moselle sediments, while ∑PAEs and ∑OPEs contents were of the same order of magnitude in the Meuse sediments. Although increases in concentrations do not evolve linearly, our results clearly indicate an increase in OPEs and PAEs concentrations from the 1950–1970 period onwards, compared with the first half of the 20th century. Our results show that, ∑OPE contents increase gradually over time in the Loire and Meuse rivers but evolve more randomly in the Moselle River. Trajectories of ∑PAEs depend on the river and no generality can be established, suggesting sedimentary reworking and/or local contamination. Data from this study allowed comparisons of contents of ∑OPEs and ∑PAEs between rivers, with ∑OPE concentrations in the Moselle River > Meuse River > Loire River, and concentrations of ∑PAEs in the Loire River > Moselle River > Meuse River. Among all PAEs, di(2-ethylhexyl) phthalate (DEHP) was the most abundant in all sediment samples, followed by diisobutyl phthalate (DiBP). Tris (2-chloroisopropyl) phosphate (TCPP) was the most abundant OPE in sediments of the three rivers. In addition, strong positive Pearson correlations were observed between organic matter (OM) parameters and OPE concentrations, and to a lesser extent, between OM parameters and PAE concentrations. This is particularly true for the Moselle River and for the Loire River, but less so for the Meuse River.

Organophosphate ester additives and microplastics in benthic compartments from the Loire estuary (French Atlantic coast)

We report the first empirical confirmation of the co-occurrence of organophosphate esters (OPEs) additives and microplastics (MPs) in benthic compartments from the Loire estuary. Higher median concentrations of MPs (3387 items/kg dw), ∑13tri-OPEs (12.0 ng/g dw) and ∑4di-OPEs (0.7 ng/g dw) were measured in intertidal sediments with predominance of fine particles, and under higher anthropogenic pressures, with a general lack of seasonality. Contrarily, Scrobicularia plana showed up to 4-fold higher ∑tri-OPE concentrations in summer (reaching 37.0 ng/g dw), and similar spatial distribution. Polyethylene predominated in both compartments. Tris(2-ethylhexyl) phosphate (TEHP), its degradation metabolite (BEHP) and tris-(2-chloro, 1-methylethyl) phosphate (TCIPP) were the most abundant OPEs in sediments, while TCIPP predominated in S. plana. The biota-sediment accumulation factors suggest bioaccumulation potential for chlorinated-OPEs, with higher exposure in summer. No significant correlations were generally found between OPEs and MPs in sediments suggesting a limited role of MPs as in-situ source of OPEs.

Spatial and temporal variability and risk assessment of organophosphate esters in seawater and sediments of the Yangtze River estuary

Organophosphate esters (OPEs) as substitutes for PBDEs have been widely detected in the marine environment, while little is known about the pollution characteristics and variation of OPEs in estuarine environments with complex hydrodynamic conditions and land-based input. Yangtze River Estuary (YRE) is a typical highly urbanized and industrialized estuary, with a complex hydrological environment and geochemical behavior. This study found that the concentrations of OPEs in both seawater and sediments in the YRE were higher in spring than in summer. Alkyl OPEs were the first contributor, with TnBP and TiBP as the main components, where the contribution of alkyl OPEs had exceeded 75 % in both seawater and sediments in spring, and 60 % in summer seawater, and even 80 % in sediments. In spring, OPEs peaked in the central to southern region near the YRE. In summer, OPEs were mainly concentrated in the southern branch waterway and southern nearshore area of the YRE and showed a decreasing trend to the northeast. The OPEs in the sediments were mainly concentrated in the Yangtze River Mud Area (YREMA) and the Zhe-Min Coastal Mud Area (ZMCMA). Based on the fugacity model and principal component analysis, sediments could be released into the aquatic environment as an endogenous source, and exogenous sources were mainly municipal and industrial sewage discharge sources, urban and marine traffic discharge sources, and atmospheric deposition sources. The ecological risk analysis showed that the Σ14OPEs had exhibited a low to moderate ecological risk in the southern branch waterway and the south-central region offshore.

Occurrence, source apportionment, and ecological risk assessment of organophosphate esters in surface sediment from the Ogun and Osun Rivers, Southwest Nigeria

Organophosphate esters (OPEs) are synthetic chemicals widely used as e.g., flame retardants and plasticisers in various consumer products. Due to the toxicity of OPEs in aquatic ecosystems, exposure of fauna and flora to these compounds is of potential concern. In this study, the concentrations, profiles, sources, and ecological risk of eight OPEs were investigated in the sediments from the two major rivers in southwest Nigeria. Concentrations of ∑OPEs in surface sediments were in the range 13.1 – 2110 ng/g dry weight (dw) (median: 378 ng/g dw) in the Ogun River and 24.7—589 ng/g dw (median: 174 ng/g dw) in the Osun River. These concentrations are broadly within the range of those reported in surface sediment in previous studies conducted in other locations around the world. Tris (2-butoxyethyl) phosphate (TBOEP) was the dominant OPE in the sediment samples with a median concentration of 337 and 126 ng/g dw for the Ogun and Osun Rivers respectively, while tri-n-butyl phosphate (TnBP) was not detected in any sample. Excluding TBOEP, the chlorinated organophosphate esters: tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) were the dominant OPEs in the Osun River, while the aryl-OPEs: triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP), and tri-m-tolyl phosphate (TMTP) were dominant in the Ogun River. Under a median exposure scenario, moderate ecological risk was predicted from exposure to TCIPP in the Osun River. In contrast, under a high exposure scenario, concentrations of TDCIPP (risk quotient, RQ = 5.33—5.37) constituted a high ecological risk in both rivers, with moderate risks observed for TBOEP (RQ = 0.022—0.18) and TCIPP (RQ = 0.097 – 0.16). Therefore, the risk to aquatic organisms from concomitant exposure to mixtures of OPEs in freshwater ecosystems requires further investigation.Graphical

Investigating the presence of organophosphate esters in sediments from a typical fishing port agglomeration in Dalian, North China

The presence of 14 organophosphate esters (OPEs) in surface sediments from a typical fishing port agglomeration in Dalian, North China was investigated for the first time. Tris(2-ethylhexyl) phosphate (TEHP), triphenylphosphine oxide (TPPO), and tris(2-chloroethyl) phosphate (TCEP) dominated 12 detectable OPEs (∑OPEs), with concentrations ranging widely from 0.56 to 352 ng/g (dry weight basis). The ∑OPE levels in sediments varied significantly across fishing harbors of various grades, and within the same grade, highlighting uneven distribution of OPE sources and inputs to harbors. The first- and second-class fishing harbors had higher geometric mean of ∑OPE contents compared to center and natural harbors, reflecting higher OPE pollution in these areas. Although there were significant correlations among the OPE congeners with high detection frequencies, the composition patterns of sediment OPEs varied considerably among fishing ports. The sediments in the center and first-class harbors had higher abundance of non-chlorinated OPEs (non-Cl-OPEs), suggesting heterogeneity in source strength and pollution characteristics of Cl- and non-Cl-OPEs in fishing ports. The distribution of OPEs in sediments was weakly associated with sediment organic carbon, but not socioeconomic variables, indicating complex controlling factors of their distributions in port sediments. The ecological risks of sediment OPEs were evaluated, and while OPE accumulations ranged broadly (7–684 ng/cm2), exposure hazards were negligible. The sediments in first- and second-class fishing harbors, which had greater OPE accumulation, were identified as reservoirs of OPEs in port aquatic environments.

Temporal trends of organophosphate esters in a sediment core from the tidal flat of Liao River estuary, Northeast China

The historical trends and inventory of organophosphate esters (OPEs) were investigated based on depth profiles of OPEs in sediment core collected from the tidal flat of the Liao River estuary in northeastern China. The concentration of ∑13OPEs in sediment core has increased continuously since records began, reaching a peak of 10.8 ng g-1 dry weight (dw) in the 1960s, then began to decline and fall to a low of 3.91 ng g-1 dw in the 1980s, before rising again and increasing to 20.4 ng g-1 dw in the 2000s. After a brief decline, It started to increase again and reached a peak of 27.0 ng g-1 dw in 2018. Tributyl-n-phosphate was found in each layer of the sediment core, accounting for 31.9 - 100% of ∑13OPEs. The fluxes of OPEs ranged from 46.5 to 105 ng cm-2 y-1 in the sediment layers deposited between 2007 and 2018. The inventory of OPEs in the sediment core was estimated to be 1541 ng cm-2. This work reports for the first time the historical contamination trends of OPEs in Chinese sediments, which is important for assessing the environmental risk of OPEs.

A review of environmental occurrence, analysis, bioaccumulation, and toxicity of organophosphate esters.

The ban and restriction of polychlorinated biphenyls (PCBs) and major brominated flame retardants (BFRs), including hexabromocyclododecane (HBCD) and polybrominated diphenyl ethers (PBDEs), due to their confirmed detrimental effects on wildlife and humans have paved the way for the wide application of organophosphate esters (OPEs). OPEs have been extensively used as alternative flame retardants, plasticizer, and antifoaming agents in various industrial and consumer products, which leads to an increase in production, usage, and discharge in the environment. We compile recent information on the production/usage and physicochemical properties of OPEs and discussed and compared the available sample treatment and analysis techniques of OPEs, including extraction, clean-up, and instrumental analysis. The occurrence of OPEs in sediment, aquatic biota, surface, and drinking water is documented. Toxicity, human exposure, and ecological risks of OPEs were summarized; toxicological data of several OPEs shows different adverse health effects on aquatic organisms and humans. Much attention was given to document evidence regarding the bioaccumulation and biomagnification potential of OPEs in aquatic organisms. Finally, identified research gaps and avenues for future studies are forwarded.

Organophosphate esters in sediment from Taihu Lake, China: Bridging the gap between riverine sources and lake sinks

Organophosphate esters in sediment from Taihu Lake, China: Bridging the gap between riverine sources and lake sinks

Environmental occurrence of phthalate and organophosphate esters in sediments across the Gulf of Lion (NW Mediterranean Sea)

Seven phthalate (PAEs) and nine organophosphate esters (OPEs) were measured in surface sediments across the Gulf of Lion (NW Mediterranean Sea) at twelve stations characterized by different anthropogenic signatures. ∑PAEs and ∑OPEs concentrations ranged from 2 to 766 ng/g DW (av. 196 ng/g DW) and from 4 to 227 ng/g DW (av. 54 ng/g DW), respectively. Our analysis of the potential sources of these organic plastic additives in sediments of the Gulf of Lion suggests that the dominant factors affecting their occurrence and environmental distribution are port-based industrial activities and urban pressures. Indeed, the highest ∑PAEs and ∑OPEs concentrations were found close to the ports of Toulon and Marseille (Estaque) and at the sites impacted by the Marseille metropolitan area (i.e. at the outlets of the waste water treatment plant at Cortiou and at the mouth of the Huveaune River). The lowest levels were generally found in protected areas (e.g. Port-Cros) and at sites relatively far from the coast. DEHP was seen to be the most abundant PAE while TDCP, TEHP and TiBP were the most abundant OPEs in the area. Our results also expose the contribution of additives entering the Gulf of Lion via sedimentary material from the Rhône River, with positive correlations between the total organic carbon (TOC) content in the sediment and the ∑PAEs and ∑OPEs concentrations. However, additive concentrations decreased from shore to offshore in the Rhône River discharge area, indicating an efficient dilution of the contaminants accumulated at the river mouth area.

Distribution, source apportionment and ecological risks of organophosphate esters in surface sediments from the Liao River, Northeast China

A total of 24 surface sediment samples were collected from Liao River, Northeast China. The concentration, spatial distribution, potential source, and ecological risk of 13 organophosphate esters (OPEs) flame retardants and plasticizers were analyzed. The total concentrations of OPEs varied considerably, ranging from 19.7 to 234 ng g−1 dry weight (dw), with the mean concentrations of 64.2 ± 52.2 ng g−1 dw. The OPEs pollution was increasing from upstream to downstream of Liao River. Compared with other sediments of rivers and lakes all over the world, Liao River has been seriously contaminated by OPEs, especially tributyl phosphate (TNBP) and tri-butoxyethyl phosphate (TBOEP). TNBP was the most abundant OPEs, followed by TBOEP and triphenylphosphine oxide. Their mean relative contributions were 26.3%, 12.4% and 11.6%, respectively. Positive matrix factorization indicated that OPEs in sediments from Liao River might be derived from plastic, textile, and polyurethane foam, anti-foam agent, hydraulic fluids, and coatings, indoor release, and chemical process emission. The risk of potential adverse effects of each individually OPEs on aquatic organisms were low (risk quotient less than 0.1). 2-Ethylhexyl diphenyl phosphate was the main substance causing risk.

Occurrence and distribution of organophosphate esters in sediment from northern Chinese coastal waters

Organophosphate esters (OPEs) are used as flame retardants and plasticizers in many consumer products. Owing to OPEs’ toxicity, exposure of organisms in aquatic ecosystems is a concern. Information that pertains to the occurrence and distribution of OPEs in marine aquatic environment, however, is scarce. In this study, concentrations and profiles of 14 OPE triesters were determined in sediment collected in coastal waters (Bohai Sea and East China Sea) of northern China. The total concentrations of OPEs (ΣOPEs) in surface sediment were in the range of 1.76–49.9 (median: 9.13) ng/g dry weight (dw), which were comparable to or lower than the range of concentrations reported for surface sediments worldwide. Tris(2-chloro-propyl) phosphate (TCIPP), tris(2-chloroethyl) phosphate (TCEP), tri-isobutyl phosphate (TiBP), and tri-n-butyl phosphate (TnBP) were the predominant OPEs found in surface sediment, collectively accounting for 81% of the total concentrations. ΣOPE concentrations in sediment core (range: 8.58–169, median: 31.6 ng/g dw) were generally higher than those found in surface sediment. The vertical distribution of OPEs in sediment core showed a gradual increasing trend in concentrations during the past decade.

Occurrence, distribution and risk assessment of organophosphate esters in surface water and sediment from a shallow freshwater Lake, China

Organophosphate esters (OPEs) are ubiquitous in the environment and pose a potential threat to ecosystem and human health. This study investigated the concentrations, distributions and risk of 12 OPEs in surface water and sediment from Luoma Lake, Fangting River and Yi River. Solid-phase extraction (SPE) method were used to extract OPEs from water samples, ultrasonic process and SPE method were used to extract OPEs from sediment samples, and the extracts were finally analyzed using the HPLC-MS/MS. The results revealed that the median and maximum concentrations of ΣOPEs were 73.9 and 1066 ng/L in surface water, and were 28.7 and 35.9 ng/g in sediment, respectively. Tris(2-chloroethyl) phosphate (TCEP) and trimethyl phosphate (TMP) were the most abundant OPEs in the surface water with median concentrations of 24.3 and 16.4 ng/L in Luoma Lake, respectively. Triethyl phosphate (TEP) was the most abundant OPE in the sediment with a median concentrations of 28.9 ng/g. However, tricresyl phosphate (TCrP) and ethylhexyl diphenyl phosphate (EHDPP) predominantly contributed to the ecological risk with respective median risk quotients 0.07 and 0.01 for surface water in Luoma Lake. TEP and TCrP were the most significant contributors to the ecological risk with respective median risk quotients of 6.4 × 10−4 and 5.6 × 10−4 for sediment. It was also found that inflowing Fangting River could be the major pollution source to Luoma Lake. The no-cancer and carcinogenic risks of OPEs were lower than the theoretical threshold of risk. The study found that the ecological and human health risks due to the exposure to OPEs were currently acceptable. In other words, the Luoma Lake was relatively safer to use as a drinking water source in urban areas in the context of OPEs pollution.

Spatiotemporal distribution and risk assessment of organophosphate esters in sediment from Taihu Lake, China.

The occurrence and spatiotemporal distribution of 12 organophosphate esters (OPEs) were investigated in the sediments collected from Taihu Lake. Compared to the same lake in 2012 (3.4-14ng/gdw), the concentrations of ∑12 OPEs in sediments ranged from 10.76 to 335.37ng/gdw and from 8.06 to 425.39ng/gdw in 2015 and in 2016, respectively, indicating that the OPEs levels in Taihu Lake have aggravated, recently. TEHP was the most abundant compound of the OPEs, which suggested that TEHP was the most widely used around Taihu Lake recently. The positive correlations between some of individual OPEs and the principal components analysis suggested the same potential sources for them. The strong positive correlation between ∑BPs and TOC content indicated that TOC content was one of the factors affected the distribution of ∑OPEs in the sediment. Risk quotient (RQ) for OPEs showed no high eco-toxicity risk in sediment for aquatic organisms.

Concentration and spatial distribution of organophosphate esters in the soil-sediment profile of Kathmandu Valley, Nepal: Implication for risk assessment

Despite the fact that soil and sediments, which act as a sink or potential source of organic pollutants, have been polluted with organophosphate esters (OPEs) around the globe, extremely constrained data is accessible on environmental concentration and fate of OPEs in solid matrices in whole of the South Asia particularly if there should be an occurrence in Nepal. In this study, surface soil (N=19) and sediments samples (N=20) were analyzed for eight different OPE in Kathmandu Valley during October 2014. The concentration of ∑8OPE measured in sediments samples was 12 times higher than soil and ranged 983–7460ng/g dw (median 2210ng/g dw) and 65–27,500ng/g dw (186ng/g dw), respectively. TMPP was most abundant in soil followed by TCIPP, TEHP and EHDPHP and ranged 17–25,300ng/g dw (41.3ng/g dw), 11.2–911ng/g dw (31.7ng/g dw), 8.52–858ng/g dw (26.1ng/g dw) and 10.2–114ng/g dw (25.6ng/g dw), respectively. TEHP was most prevalent in sediments followed by TMPP and EHDPHP and were in the range of 657–3020ng/g dw (median 1140ng/g dw), 267–2630ng/g dw (median 815g/g dw), 34–418ng/g (median 131ng/g dw), respectively. The sources of the high level of OPEs in soil was related to the end point use of consumer materials, traffic emission, and close proximity to commercial and industrial areas; while domestic sewage discharges and effluents from carpet industry were identified as the possible entry of OPE in sediments. Total organic carbon (TOC) and black carbon (BC) content in soil were moderately and positively correlated with ∑8OPE indicating more or less influence of soil organic carbon. The health risk assessment suggested dermal absorption of OPEs via soil is the primary pathway of human exposure to the general population. The significantly high-risk quotient (RQ) estimated for ∑8OPEs especially TMPP and TPHP suggested significant potential adverse risk for aquatic organisms.

Organophosphate Esters in Sediment of the Great Lakes.

This is the first study on organophosphate ester (OPEs) flame retardants and plasticizers in the sediment of the Great Lakes. Concentrations of 14 OPEs were measured in three sediment cores and 88 Ponar surface grabs collected from Lakes Ontario, Michigan, and Superior of North America. The sum of these OPEs (Σ14OPEs) in Ponar grabs averaged 2.2, 4.7, and 16.6 ng g-1 dw in Lakes Superior, Michigan, and Ontario, respectively. Multiple linear regression analyses demonstrated statistically significant associations between logarithm concentrations of Σ14OPEs as well as selected congeners in surface grab samples and sediment organic carbon content as well as a newly developed urban distance factor. Temporal trends observed in dated sediment cores from Lake Michigan demonstrated that the recent increase in depositional flux to sediment is dominated by chlorinated OPEs, particularly tris(2-chloroisopropyl) phosphate (TCPP), which has a doubling time of about 20 years. Downward diffusion within sediment may have caused vertical fractionation of OPEs over time. Two relatively hydrophilic OPEs including TCPP had much higher concentrations in sediment than estimated based on equilibria between water and sediment organic carbon. Approximately a quarter (17 tonnes) of the estimated total OPE burden (63 tonnes) in Lake Michigan resides in sediment, which may act as a secondary source releasing OPEs to the water column for years to come.

Analysis of Organophosphate Esters in Sediment Samples Using Gas Chromatography-Tandem Mass Spectrometry

Abstract An efficient extraction and purification method coupled to gas chromatography-tandem mass spectrometry (GC-MS/MS) with electron impact (EI) was developed to determine eight organophosphate esters (OPEs) in sediment samples. OPEs were extracted from the sediments through vortex oscillation for 1 min and ultrasonic extraction using 20 mL of n-hexane and acetone mixture (1:1, V/V) for 10 min, followed by purification by Florisil solid phase extraction (SPE) column and quantitative determination by GC-MS/MS. The result showed that this pretreatment method was simple and less solvent consumption. At three spiked levels of 10, 20 and 50 μg L−1, the recovery of OPEs (except TEP) was between 80% and 120%, and the limits of detection for OPEs were 0.31 to 64.51 ng L−1, showing a good precision and accuracy in the determination of OPEs in sediment.