Log KOC Research Articles

Assessment of impacts of diphenyl phosphate on groundwater and near-surface environments: Sorption and toxicity

Wastewater recovered from hydraulic fracturing is referred to as flowback and produced water (FPW), and is often saline, contains numerous organic and inorganic constituents, and may pose threats to groundwater resources. Hundreds of spills of FPW have been reported to the Alberta Energy Regulator each year. Recently, samples of FPW derived from hydraulic fracturing of the Duvernay Formation, AB, were found to contain a previously unidentified class of aryl phosphates, including diphenyl phosphate (DPP), triphenyl phosphate (TPP), and others. Aryl phosphates are also used in a variety of other industries and their constituents can be found in flame retardants, plasticizers, lubricants, hydraulic fluids, and oxidizers. Many of these aryl phosphates break down into DPP. Therefore, it is important to determine the environmental fate and potential impact of DPP if spilled in the near-surface, as DPP is an emerging contaminant in soil and groundwater systems. This study was aimed at determining 1) the sorption behavior of DPP onto various surficial sediments collected within the Fox Creek, AB region, and 2) the toxicity of DPP toward aquatic ecosystems. We report that the sorption of DPP onto both clay-rich soils and sandy sediment was low compared to that of other aryl phosphates, with an average log KOC value of 2.30 ± 0.42 (1σ). Therefore, the transport of DPP in groundwater would be rapid due to its low degree of sorption on surficial materials. We also determined the acute 96 h-LC50 of DPP on zebrafish embryos to be 50.0 ± 7.1 mg/L. Su et al. (2014) studied the toxic effects of DPP and TPP on chicken embryonic hepatocytes and found that DPP had less cytotoxic effects than TPP but altered more gene transcripts. From the results our study, we infer that DPP may pose an environmental risk to aquatic ecosystems if released into the environment.

Occurrence and partitioning behavior of perfluoroalkyl acids in wastewater effluent discharging into the Long Island Sound

Perfluoroalkyl acids (PFAAs) were measured in aqueous and suspended particulate matter (SPM) fractions in the final effluents from 12 wastewater treatment facilities located around the Connecticut shoreline. Aqueous phase concentrations ranged from 53 to 198 ng/L for ∑PFAAs with ≤7 perfluorinated carbons (CF2) and 2–73 ng/L for >7 CF2 PFAAs. Predominant PFAAs associated with effluent derived SPM were perfluorodecanoic acid and perflurorooctane sulfonic acid, detected in 48% and 52% of samples in concentrations ranging from <LOQ–1770 ng/g and <LOQ–2750 ng/g respectively. Based on the range of concentrations detected and the average flow of final effluent to the Long Island Sound (LIS), average total annual PFAA mass loads from wastewater treatment facilities to the LIS is estimated in the range of 70–315 kg/year, with 4–100 kg/year consisting of >7 CF2 PFAAs. Partitioning coefficients (log KOC) derived for effluent water and SPM phases (4.2 ± 0.3, 4.4 ± 0.4, 5.1 ± 0.2 and 5.3 ± 0.2 for PFOA, PFNA PFDA and PFUnA; 4.5 ± 0.2 and 5.2 ± 0.2 for PFOS and PFHsX respectively) were found to be of similar magnitude to aeration tank particles, though 0.5 to 2 log units greater than sludge solids and to natural system particulates including riverine SPM, estuarine SPM and sediments. Results from this study suggest that effluent derived suspended particulate matter could be an effective vector in the transport of long-chained PFAAs through wastewater treatment into receiving waters, and a potential vector to the local food chain.

Nanopore-filling effect of phenanthrene sorption on modified black carbon

Black carbon was produced by slow pyrolysis under an oxygen-limited condition at 500 °C, and was modified by some chemical methods (oxidation, hydrolysis, activation, and surface recombination). The modified samples were characterized by using elemental analysis, Fourier transformed infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) surface analysis, Boehm titration, cation exchange capacity(CEC)analysis, CO2 adsorption analysis, and then used to investigate the sorption behavior of phenanthrene. The results showed that the activation of ZnCl2 gave a maximum nanopore volume of 96.5 μL/g and a specific surface area of 241 m2/g, while the oxidation of NaClO gave a minimum nanopore volume of 63.3 μL/g and a specific surface area of 158 m2/g. The FTIR, XPS, and Boehm titration analysis showed that the new oxygen-containing functional groups were introduced during the oxidation treatments of H2O2 and NaClO. The sorption of phenanthrene on all samples was typically nonlinear, and the nonlinear factor (n) was negatively correlated with Vo, especially with Vo at 0–1.1 nm. The sorption parameter (log KOC) was positively correlated with nanopore volume (Vo) and specific surface area (SSA). Moreover, the model analysis showed that the nanopore filling was the main sorption mechanism, and molecular sieve effect was observed in the sorption of phenanthrene.

DDT and related compounds in pore water of shallow sediments on the Palos Verdes Shelf, California, USA

Abstract For nearly two and a half decades following World War II, production wastes from the world's largest manufacturer of technical DDT (1-chloro-4-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene) were discharged into sewers of Los Angeles County. Following treatment, the wastes were released via a submarine outfall system to nearshore coastal waters where a portion accumulated in shallow sediments of the Palos Verdes Shelf (PVS). An investigation of the pore-water geochemistry of DDT-related compounds (DDX) was undertaken in an effort to understand factors controlling the rate of reductive dechlorination (RDC) of the major DDT degradate, 4,4′-DDE (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene). Equilibrium matrix-solid phase microextraction (matrix-SPMEeq) combined with automated thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) was used to determine freely dissolved concentrations of ten DDX analytes in sediment cores collected from three locations on the PVS (stations 3C, 6C, 8C, which are 7 km, 2 km, and 0 km, respectively, downcurrent from the outfall system). Pore-water concentrations (pM) of the principal DDX compounds involved in RDC were: 3C-DDE: 6.0–24, DDMU (1-chloro-4-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene): 11–160, DDNU (1-chloro-4-[1-(4-chlorophenyl)ethenyl]benzene): 1.8–68; 6C-DDE: 5.6–170, DDMU: 5.6–177, DDNU: 1.7–87; 8C-DDE: 27–212, DDMU: 31–403, DDNU: 5.5–89. Variations in the spatial distribution of DDX analytes in pore water reflect several factors including proximity to the outfalls, RDC reaction rates, and natural variability in sedimentation and post-depositional transport processes. A comparison of pore-water data produced using matrix-SPMEeq/TD-GC/MS and whole-core squeezing/solvent extraction/liquid injection-GC/MS indicates that the majority of the DDE in the upper sediment column (≤about 10 cm) is associated with dissolved/colloidal organic matter. Below that depth, freely-dissolved DDE predominates. The principal organic geochemical phase controlling sorption of DDE in PVS sediments are residual hydrocarbons, the vast majority of which originated from petroleum refinery wastes. Organic carbon-normalized sediment-water distribution coefficients (KOC) were calculated from solid-phase and pore-water concentrations of DDX and organic carbon. Log KOC values (L/kg) were relatively invariant across the shelf and with depth in the sediment column. Shelf-wide compound-specific coefficients (log KOC) were: DDE: 7.5 ± 0.11, DDMU: 6.92 ± 0.13, DDNU: 6.37 ± 0.19. The spatial uniformity of KOC means that biological exposure and availability of the DDX compounds can, in principle, be estimated from solid-phase chemical measurements.

Sorption of perfluoroalkyl substances (PFASs) to an organic soil horizon – Effect of cation composition and pH

Accurate prediction of the sorption of perfluoroalkyl substances (PFASs) in soils is essential for environmental risk assessment. We investigated the effect of solution pH and calculated soil organic matter (SOM) net charge on the sorption of 14 PFASs onto an organic soil as a function of pH and added concentrations of Al3+, Ca2+ and Na+. Often, the organic C-normalized partitioning coefficients (KOC) showed a negative relationship to both pH (Δlog KOC/ΔpH = −0.32 ± 0.11 log units) and the SOM bulk net negative charge (Δlog KOC = −1.41 ± 0.40 per log unit molc g−1). Moreover, perfluorosulfonic acids (PFSAs) sorbed more strongly than perfluorocarboxylic acids (PFCAs) and the PFAS sorption increased with increasing perfluorocarbon chain length with 0.60 and 0.83 log KOC units per CF2 moiety for C3–C10 PFCAs and C4, C6, and C8 PFSAs, respectively. The effects of cation treatment and SOM bulk net charge were evident for many PFASs with low to moderate sorption (C5–C8 PFCAs and C6 PFSA). However for the most strongly sorbing and most long-chained PFASs (C9–C11 and C13 PFCAs, C8 PFSA and perfluorooctane sulfonamide (FOSA)), smaller effects of cations were seen, and instead sorption was more strongly related to the pH value. This suggests that the most long-chained PFASs, similar to other hydrophobic organic compounds, are preferentially sorbed to the highly condensed domains of the humin fraction, while shorter-chained PFASs are bound to a larger extent to humic and fulvic acid, where cation effects are significant.

Occurrence, partitioning and bioaccumulation of emerging and legacy per- and polyfluoroalkyl substances in Taihu Lake, China

There are many studies about the occurrence of legacy perfluoroalkyl acids (PFAAs) in fresh water ecosystem, but related information about emerging per- and polyfluoroalkyl substances (PFASs) is limited. In this study, along with ten legacy PFAAs, twelve non-PFAAs, including precursors of perfluorooctane sulfonic acid (PFOS) and emerging PFASs in the water, sediment and organisms in Taihu Lake, China, were investigated. As one replacement product of PFOS, perfluorohexane sulfonic acid (PFHxS) (mean: 69.3ng/L) was the predominant PFAA in the water samples. Perfluorooctanesulfonamide (PFOSA) (mean: 0.190ng/L) and 6:2 fluorotelomer phosphate diester (6:2 diPAP) (0.034ng/L) were detected in all the water samples. Other emerging PFASs, such as N-ethyl perfluorooctanesulfonamidoa-cetic acid (NEtFOSAA), bis(perfluorohexyl) phosphinic acid (6:6 PFPiA) were frequently detected in the sediment and/or organisms. The organic carbon normalized sediment-water distribution coefficients (KOC) and bioaccumulation factors (BAFs) of the PFASs generally increased with their log KOW values. However, PFOSA, NEtFOSAA, 6:2 diPAP and 6:6 PFPiA displayed lower log BAFs, and/or lower log KOC than expected, which may be due to biotransformation potentials and/or large molecular size. PFOSA was not biomagnified in the food web. For other emerging PFASs, the low detection frequencies in the organisms hampered us to evaluate their biomagnification potentials. The lower percentage of most of the branched PFOS isomers while higher percentage of 1m-PFOS in the organisms suggested that there was indirect source of PFOS in the organisms. Similar to PFOS and PFOA, linear PFHxS isomer was preferentially enriched in organisms relative to its branched isomers.

Sorption and bioaccumulation behavior of multi-class hydrophobic organic contaminants in a tropical marine food web

While numerous studies have demonstrated the environmental behavior of legacy persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), information regarding sorption and bioaccumulation potential of other widely used organic chemicals such as halogenated flame retardants (HFRs) is limited. This study involved a comprehensive field investigation of multi-class hydrophobic organic contaminants (HOCs) in environmental media and fish in Singapore Strait, an important tropical maritime strait in Southeast Asia. In total, 90 HOCs were analyzed, including HFRs, synthetic musks, PCBs, OCPs, as well as triclosan and methyl triclosan. The results show that the organic carbon normalized sediment-seawater distribution ratios (CSED/CWD) of the studied compounds are comparable to the organic carbon-water partition coefficients (KOC), over a log KOC range of approximately 4–11. The observed species-specific bioaccumulation factors (BAFs), biota-sediment accumulation factors (BSAFs), organism-environment media fugacity ratios (fFISH/fWD and fFISH/fSED) and trophic magnification factors (TMFs) indicate that legacy POPs and PBDE 47 show bioaccumulation behavior in this tropical marine ecosystem, while triclosan, tonalide, dodecachlorodimethanodibenzocyclooctane stereoisomers (DDC-COs), and hexabromocyclododecanes (HBCDDs) do not. Methyl triclosan and galaxolide exhibit moderate biomagnification. Tetrabromobisphenol A (TBBPA) and 1,2-bis (2,4,6-tribromophenoxy)ethane (BTBPE) were detected in environmental media but not in any of the organisms, suggesting low bioaccumulation potential of these flame retardants. The apparently low bioaccumulation potential of the studied HFRs and synthetic musks is likely because of metabolic transformation and/or reduced bioavailability due to the hydrophobic nature of these compounds.

Occurrence and distribution of halogenated flame retardants in an urban watershed: Comparison to polychlorinated biphenyls and organochlorine pesticides

Due to restrictions on polybrominated diphenyl ethers (PBDEs), market demand for alternative flame retardants is projected to increase, worldwide. Information regarding the environmental behavior of these compounds is limited. The present study involved field measurements of several alternative halogenated flame retardants (HFRs), along with PBDEs and legacy persistent organic pollutants (POPs) in surface water, bottom sediments and suspended particulate matter (SPM) within a highly urbanized watershed in Singapore. Several alternative HFRs were detected in water and sediments. Dechlornane Plus stereoisomers (syn- and anti-DP) were detected in all samples, exhibiting relatively high concentrations in water, sediments and SPM. The maximum syn-DP concentrations in water, sediments and SPM were 24.30 ng/L, 2.48 ng/g dry wt. and 7774 ng/g dry wt., respectively. 1,2-Bis(2,4,6-tribromophenoxy) ethane (BTBPE), pentabromotoluene (PBT), hexabromobenzene (HxBBz) and tetrabromoethylcyclohexane (TBECH) were routinely detected. PBDE concentrations were relatively low and often non-detectable. Polychlorinated biphenyl (PCB) concentrations ranged from 0.017 to 8.37 ng/L in water, 9.86–27.92 ng/g dry wt. in SPM, and 6.48–212.3 ng/g dry wt. in sediments. Congener and isomer patterns suggested no recent inputs of PBDEs or dichlorodiphenyltrichloroethane (DDT). Rainfall was found to be an important factor influencing temporal and spatial patterns of DPs, BTBPE, PBDEs and some organochlorines in surface water. Land use index was found to be important for several organochlorines, but not HFRs. The observed sediment-water partitioning behavior of the studied HFRs and legacy POPs was highly dependent on chemical hydrophobicity. The data demonstrate that the studied HFRs have a relatively high affinity for SPM and bottom sediments. For example, the log KOC,OBS for TBECH, syn-DP and anti-DP and BTBPE in bottom sediments ranged between 8.1 and 9.6. The findings will aid future studies regarding fate, transport and bioaccumulation of these current-use contaminants of concern.

A flow-through aqueous standard generation system for thin film microextraction investigations of UV filters and biocides partitioning to different environmental compartments

In this paper problems associated with preparation of aqueous standard of highly hydrophobic compounds such as partial precipitation, being lost on the surfaces, low solubility in water and limited sample volume for accurate determination of their distribution coefficients are addressed. The following work presents two approaches that utilize blade thin film microextraction (TFME) to investigate partitioning of UV filters and biocides to humic acid (dissolved organic carbon) and sediment. A steady-state concentration of target analytes in water was generated using a flow-through aqueous standard generation (ASG) system. Dialysis membranes, a polytetrafluoroethylene permeation tube, and a frit porous (0.5 μm) coated by epoxy glue were basic elements used for preparation of the ASG system. In the currently presented study, negligible depletion TFME using hydrophilic-lipophilic balance (HLB) and octadecyl silica-based (C18) sorbents was employed towards the attainment of free concentration values of target analytes in the studied matrices. Thin film geometry provided a large volume of extraction phase, which improved the sensitivity of the method towards highly matrix-bound analytes. Extractions were performed in the equilibrium regime so as to prevent matrix effects and with aims to reach maximum method sensitivity for all analytes under study. Partitioning of analytes on dissolved organic carbon (DOC) was investigated in ASG to facilitate large sample volume conditions. Binding percentages and DOC distribution coefficients (Log KDOC) ranged from 20 to 98% and 3.71–6.72, respectively. Furthermore, sediment-water partition coefficients (Kd), organic-carbon normalized partition coefficients (Log KOC), and DOC distribution coefficients (Log KDOC) were investigated in slurry sediment, and ranged from 33 to 2860, 3.31–5.24 and 4.52–5.75 Lkg-1, respectively. The obtained results demonstrated that investigations utilizing ASG and TFME can yield reliable binding information for compounds with high log KOW values. This information is useful for study of fate, transport, and ecotoxicological effects of UV filters and biocides in aquatic environment.

The importance of nano-porosity in the stalk-derived biochar to the sorption of 17β-estradiol and retention of it in the greenhouse soil.

Natural estrogens in greenhouse soils with long-term manure application are becoming a potential threat to adjacent aquatic environment. Porous stalk biochar as a cost-effective adsorbent of estrogen has a strong potential to reduce their transportation from soil to waters. But the dominant adsorption mechanism of estrogen to stalk biochars and retention of estrogen by greenhouse soils amended with biochar are less well known. Element, function groups, total surface area (SAtotal), nano-pores of stalk biochars, and chemical structure of 17β-estradiol (E2, length 1.20nm, width 0.56nm, thickness 0.48nm) are integrated in research on E2 sorption behavior in three stalk-derived biochars produced from wheat straw (WS), rice straw (RS), and corn straw (CS), and greenhouse soils amended with optimal biochar. The three biochars had comparable H/C and (O + N)/C, while their aromatic carbon contents and total surface areas (SAtotal) both varied as CS > WS > RS. However, WS had the highest sorption capacity (logK oc), sorption affinity (K f ), and strongest nonlinearity (n). Additionally, the variation of Langmuir maximum adsorption capacity (Q 0) was consistent with the trend for SA1.2-20 (WS > RS > CS) but contrary to the trend for SAtotal and SA<1.2 (CS > WS > RS). These results indicate that pore-filling dominates the sorption of E2 by biochars and exhibits "sieving effect" and length-directionality-specific via H-bonding between -OH groups on the both ends of E2 in the length direction and polar groups on the inner surface of pores. After the addition of wheat straw biochar, the extent of increase in the sorption affinity for E2 in the soil with low OC content was higher than those in the soil with high OC content. Therefore, the effectiveness for the wheat straw biochar mitigating the risk of E2 in greenhouse soil depended on the compositions of soil, especially organic matter.

The influence of particles on bioavailability and toxicity of pesticides in surface water.

Environmental risk assessment is an essential part of the approval process for pesticides. Exposure concentrations are compared with ecotoxicological data obtained from standardized laboratory studies and, if available, from field studies to determine the risk of a substance or formulation for aquatic communities. Predicted concentrations in surface waters are derived using, for example, the European FOrum for the Co-ordination of pesticide fate models and their USe (FOCUS) or the German Exposit models, which distinguish between exposure to dissolved and particle-associated pesticide concentrations, because the dissolved concentration is thought to be the best predictor of bioavailability and toxicity. Water and particle-associated concentrations are estimated based on the organic carbon-water partitioning coefficient (KOC ). This review summarizes published information on the influence of natural suspended solids on bioavailability and toxicity of pesticides to aquatic organisms (algae, invertebrates and fish), and the value of log KOC and log KOW (octanol-water coefficient) as sole predictors of the bioavailable fraction is discussed. The information showed that: 1) the quality and origin of suspended solids played an important role in influencing pesticide bioavailability and toxicity; 2) a decrease in toxicity due to the presence of suspended solids was shown only for pyrethroid insecticides with log KOW greater than 5, but the extent of this reduction depended on particle concentration and size, and potentially also on the ecotoxicological endpoint; 3) for pesticides with a log KOW less than 3 (e.g., triazines, carbamates, and organophosphates), the impact of particles on bioavailability and toxicity is small and species dependent; and 4) pesticide bioavailability is greatly influenced by the test species and their physiology (e.g., feeding behavior or digestion). We conclude that exposure of aquatic organisms to pesticides and environmental risk of many pesticides might be underestimated in prospective risk assessment, when predicted environmental concentration is estimated based on the KOC of a compound. Integr Environ Assess Manag 2017;13:585-600. © 2016 SETAC.

Feasible preparation and characterization of tunable novel montmorillonite/block-copolymers based composites as potential dual adsorbent candidates

This study was mainly focused on exploring the possible intercalation of block-(diblock or triblock) copolymers into montmorillonite (Mt) to obtain clay mineral polymer nanocomposites (CPN) aiming to increase the interlayer space and application of Mt. The extent of the effect on interlayer space of Mt during reaction was studied in details. N2 adsorption isotherms and X-ray diffraction (XRD) studies were used to confirm the formation of CPN. It was found that the intercalation of polymers enhanced the interlayer space of Mt along with a shift of [001] plane 2θ (6.8°) to lower values. The corresponding interlayer space was increased from 12.65Å to 40.85Å. The intercalation of polymers to form CPN favors both structural orientations and functional groups for the preferential adsorption of both ionic (cationic and anionic inorganic) and non-ionic (organic, NOC) pollutants. Uptake of both organic (toluene; ethylbenzene; and xylene; in brief TEX) and inorganic (Cu2+, Pb2+ and Cr2O72−) pollutants were explored and highlighted in this study. The observed log KOC values for the distribution of organic pollutants onto CPN are significantly high in this study. In all cases the adsorption of Pb2+ was comparatively larger than that of Cu2+. Among all the obtained CPN, M-D-DMF displayed enhanced adsorption of both organic and inorganic pollutants and hence it was concluded as a potential candidate.

Occurrence and distribution of perfluoroalkyl acids (PFAAs) in surface water and sediment of a tropical coastal area (Bay of Bengal coast, Bangladesh)

This study reports the first evidence of perfluoroalkyl acids (PFAAs) in surface waters and sediments collected from the coastal area of Bangladesh. Fifteen target PFAAs, including C4–14-PFCAs (perfluoroalkyl carboxylates) and C4, C6, C8, and C10-PFSAs (perfluoroalkyl sulfonates), were quantified by HPLC–MS/MS. The ΣPFAAs in surface water and sediment samples were in the range of 10.6 to 46.8ng/L and 1.07 to 8.15ng/gdw, respectively. PFOA in water (3.17–27.8ng/L) and PFOS in sediment samples (0.60–1.14ng/gdw) were found to be the most abundant PFAAs, and these concentrations were comparable to or less than most other reported values, particularly those recorded from the coastal areas of China, Japan, Korea and Spain. The majority of the monitored PFAAs did not show clear seasonal variation. The southeastern part (Cox’s Bazar and Chittagong) of the Bangladeshi coastal area was more contaminated with PFAAs than the southern (Meghna Estuary) and southwestern parts (Sundarbans). Industrial and municipal wastewater effluents, ship breaking and port activities were identified as potential sources of the PFAA contamination in this region. Field-based sediment water distribution coefficients (KD) were calculated and corrected for organic carbon content (KOC), which reduced the variability between samples. The values of log KD (1.63–2.88) and log KOC (4.02–5.16) were higher than previously reported values, which may indicate that the partitioning of PFAAs in a tropical coastal ecosystem is different from other ecosystems, such as temperate and sub-tropical regions. Although a preliminary environmental hazard assessment indicated that PFOA or PFOS levels do not currently exceed the acute safety thresholds, we should keep in mind that they are bioavailable and can accumulate in the food chain. Therefore, the ubiquity of PFAAs in the coastal area of Bangladesh warrants further studies characterizing their specific sources and the potential long-term risks they present to both humans and wildlife.

The partitioning behavior of persistent toxicant organic contaminants in eutrophic sediments: Coefficients and effects of fluorescent organic matter and particle size

In the shallow lakes, the partitioning of organic contaminants into the water phase from the solid phase might pose a potential hazard to both benthic and planktonic organisms, which would further damage aquatic ecosystems. This study determined the concentrations of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), and phthalate esters (PAEs) in both the sediment and the pore water from Lake Chaohu and calculated the sediment – pore water partition coefficient (KD) and the organic carbon normalized sediment – pore water partition coefficient (KOC), and explored the effects of particle size, organic matter content, and parallel factor fluorescent organic matter (PARAFAC-FOM) on KD. The results showed that log KD values of PAHs (2.61–3.94) and OCPs (1.75–3.05) were significantly lower than that of PAEs (4.13–5.05) (p < 0.05). The chemicals were ranked by log KOC as follows: PAEs (6.05–6.94) > PAHs (4.61–5.86) > OCPs (3.62–4.97). A modified MCI model can predict KOC values in a range of log 1.5 at a higher frequency, especially for PAEs. The significantly positive correlation between KOC and the octanol – water partition coefficient (KOW) were observed for PAHs and OCPs. However, significant correlation was found for PAEs only when excluding PAEs with lower KOW. Sediments with smaller particle sizes (clay and silt) and their organic matter would affect distributions of PAHs and OCPs between the sediment and the pore water. Protein-like fluorescent organic matter (C2) was associated with the KD of PAEs. Furthermore, the partitioning of PARAFAC-FOM between the sediment and the pore water could potentially affect the distribution of organic pollutants. The partitioning mechanism of PAEs between the sediment and the pore water might be different from that of PAHs and OCPs, as indicated by their associations with influencing factors and KOW.

Evaluating the Salting-Out Effect on the Organic Carbon/Water Partition Ratios (KOC and KDOC) of Linear and Cyclic Volatile Methylsiloxanes: Measurements and Polyparameter Linear Free Energy Relationships

Dissolved inorganic salts influence the partitioning of organic chemicals between water and sorbents. We present new measurements of the salting-out constants (Ks) for partition ratios between water and organic carbon (KOC) and between water and dissolved organic carbon (KDOC) of three cyclic volatile methylsiloxanes (cVMS), two linear volatile methylsiloxanes (lVMS), three polychlorinated biphenyls (PCBs), and α-hexachlorocyclohexane (α-HCH). Ks, KOC, and KDOC were derived from volatilization rates of the chemicals from mixtures of water and organic carbon with varying concentrations of sodium chloride in a purge-and-trap system. KOC and KDOC values at different salinities were determined by fitting their values to reproduce observed volatilization rates using a fugacity-based multimedia model and assuming first-order kinetics for volatilization. The Ks values of cVMS and lVMS ranged from 0.16–0.76. The log KOC of cVMS and lVMS in fresh water interpolated from our measurements ranged from 5.20 to 7.36 an...

QSAR models for predicting octanol/water and organic carbon/water partition coefficients of polychlorinated biphenyls

Quantitative structure–property relationship modelling can be a valuable alternative method to replace or reduce experimental testing. In particular, some endpoints such as octanol–water (KOW) and organic carbon–water (KOC) partition coefficients of polychlorinated biphenyls (PCBs) are easier to predict and various models have been already developed. In this paper, two different methods, which are multiple linear regression based on the descriptors generated using Dragon software and hologram quantitative structure–activity relationships, were employed to predict suspended particulate matter (SPM) derived log KOC and generator column, shake flask and slow stirring method derived log KOW values of 209 PCBs. The predictive ability of the derived models was validated using a test set. The performances of all these models were compared with EPI Suite™ software. The results indicated that the proposed models were robust and satisfactory, and could provide feasible and promising tools for the rapid assessment of the SPM derived log KOC and generator column, shake flask and slow stirring method derived log KOW values of PCBs.

Shifts in production of perfluoroalkyl acids affect emissions and concentrations in the environment of the Xiaoqing River Basin, China

Perfluoroalkyl acids (PFAAs) have been widely used in surfactant applications, especially as processing acids for fluoropolymer production. This study provides an analysis of sources of certain PFAAs emitted from the intensive fluoropolymer facilities in the Xiaoqing River Basin of China. Concentrations of perfluorooctanoic acid (PFOA) as great as 0.97mg/L in surface water and 10.5μg/g dry weight in surface sediment have been detected near the effluent of one facility (F1) that produces polytetrafluoroethylene (PTFE) and other fluoropolymers with massive capacity. With the great emission of PFAAs to water in natural conditions, the log KOC values decreased for short-chain PFCAs. Mass loads of PFAAs indicated that emissions of PFAAs from other facilities or sources were much less than those from F1, which emitted 174kg/d of PFAAs including 159kg/d of PFOA to the rivers. Even though production and emissions of PFOA have been strictly controlled in other countries since 2006, production of PFOA as well as several other fluoropolymers that use PFOA as processing aids has been increasing at F1 in recent years. We recommended that production shift should be taken into consideration in PFOA elimination actions.

Bioaccumulation of pharmaceuticals and personal care products in the unionid mussel Lasmigona costata in a river receiving wastewater effluent.

Freshwater mussels are frequently found in rivers receiving effluent from wastewater treatment plants (WWTP), and there is strong evidence that poor water quality is deleterious to freshwater mussel populations. WWTPs are among the main sources of pharmaceuticals and personal care products (PPCPs) in surface waters. We monitored 145 PPCPs in wild and caged mussels both upstream and downstream of the Kitchener WWTP in the Grand River, Ontario, as well as 118 PPCPs in water samples. Our objectives were to characterize the seasonal changes in PPCP concentrations in water, to calculate bioaccumulation factors (BAFs) of PPCPs in mussels, and to determine the chemical and physical properties of PPCPs driving the bioaccumulation. Seventy PPCPs were detected in water, and concentrations were highest in the summer or early fall, which corresponded to low river flow. Forty-three PPCPs from many pharmaceutical classes were detected in mussel tissues, including stimulants, a contrasting agent, anti-inflammatory drugs, anti-bacterial agents, antibiotics, antidepressants, antihistamines, progestins, and illicit drugs such as cocaine and amphetamines. The BAFs ranged from 0.66 for metformin to 32,022 for sertraline. Using partial least squares to predict BAFs based upon chemical properties, log KOC, Log KOW, and fugacity ratio (sediment) all had similar and positive loadings with BAFs (R(2)X = 0.70; caged mussels). BAFs of PPCPs in mussels were predictable from fugacity models that estimate bioconcentration factors using log KOW. Our study demonstrated that mussels readily bioaccumulate PPCPs, in a manner consistent with expectations based upon BCF models and the chemical characteristics of each compound.

Organic Carbon/Water and Dissolved Organic Carbon/Water Partitioning of Cyclic Volatile Methylsiloxanes: Measurements and Polyparameter Linear Free Energy Relationships.

The sorption of cyclic volatile methyl siloxanes (cVMS) to organic matter has a strong influence on their fate in the aquatic environment. We report new measurements of the partition ratios between freshwater sediment organic carbon and water (KOC) and between Aldrich humic acid dissolved organic carbon and water (KDOC) for three cVMS, and for three polychlorinated biphenyls (PCBs) that were used as reference chemicals. Our measurements were made using a purge-and-trap method that employs benchmark chemicals to calibrate mass transfer at the air/water interface in a fugacity-based multimedia model. The measured log KOC of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were 5.06, 6.12, and 7.07, and log KDOC were 5.05, 6.13, and 6.79. To our knowledge, our measurements for KOC of D6 and KDOC of D4 and D6 are the first reported. Polyparameter linear free energy relationships (PP-LFERs) derived from training sets of empirical data that did not include cVMS generally did not predict our measured partition ratios of cVMS accurately (root-mean-squared-error (RMSE) for logKOC 0.76 and for logKDOC 0.73). We constructed new PP-LFERs that accurately describe partition ratios for the cVMS as well as for other chemicals by including our new measurements in the existing training sets (logKOC RMSEcVMS: 0.09, logKDOC RMSEcVMS: 0.12). The PP-LFERs we have developed here should be further evaluated and perhaps recalibrated when experimental data for other siloxanes become available.

Sorption kinetics of isoproturon and assessment of its Ecotoxicity on Lemna minor

The study was carried out to investigate the ecotoxicity of Isoproturon on Lemna minor and the interaction of the EC50 value of the chemical with sorption behaviour of the chemical in soil. The sorption isotherms (Kf and KOC) for Isoproturon were determined for three different soils having various organic carbon and clay content. EC50 for Lemna was determined both with and without soil. Both the Freundlich adsorption coefficient (Kf) and normalized sorption coefficient (KOC) values varied with different types of soil. There was moderate correlation between the log Kf and log KOC existed. The regression study revealed a strong relationship between log KOC and organic carbon and between log KOC and soil clay content. There EC50 value for Lemna grown with soil was higher than that grown without soil. However, the difference was statistically insignificant. Greater degree of inconsistency in various data suggests the reiteration of the study.DOI: http://dx.doi.org/10.3329/ralf.v1i1.22347 Res. Agric., Livest. Fish.1(1): 13-18, Dec 2014