Regression models for octanol‐water partition coefficients,and for bioconcentration in fish

Octanol‐water partition coefficients (P) of a number of organochlorine insecticides (OCs) are presented. The merits of log‐log regressions between experimental ? values and calculated estimates of P, solute activity coefficients in water, solute molecular surface area data, and reversed‐phase liquid‐chromatographic net retention data, are critically evaluated for several classes of pollutants: polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes, chlorinated biphenyls and OCs. Special attention is paid to the predictive accuracy of such semi‐empirical regressions in connection with possible effects of solute molecular shape and polarity.

Finally, bioconcentration and ‐accumulation of hydrophobic pollutants in fish are briefly discussed.     

Adsorption of pesticides by salorthids and camborthids of Punjab,Pakistan

This study was conducted to examine adsorption of pesticides bifenthrin, carbosulfan, λ-cyhalothrin, cypermethrin, endosulfan, parathion methyl, monocrotophos and 4-nitrophenol by sandy clay loam (S.C.L) and sandy loam (S.L) soils (with varying organic content). There was no significant difference between the observed soil water partitioning coefficient values (K _d) derived from linear and nonlinear Freundlich isotherms. Adsorption of pesticides on S.C.L soils was higher than those on S.L soils. K _d values showed significant correlations (r ²?=?0.8???0.99 and 0.65???0.97) with soil organic carbon content (OC) and weak correlations (r ²?=?0.2???0.29 and 0.1???0.18) with clay contents of S.C.L and S.L soil at p?≤?0.05, respectively for all pesticides (except monocrotophos). Observed K _oc values (soil-water partitioning constants based on the organic C fraction of the soil) were in accordance with the literature values of Wauchope and Tomlin with a maximum deviation of less than 0.5 log units. Ten Quantitative Property-Property Relationships (QPPR) among water solubility, n-octanol water coefficient (K _ow) and K _oc were proposed for studied pesticides except monocrotophos. The models were considered acceptable when predicted-observed difference for log?K _ow and log?K _oc were ≤?0.3 and ≤?0.5?log units, respectively, during the validation procedure. This work indicates that the log?K _oc derived from the log K_ow, from some of existing relationships, may be a fair predictor where observed values (i.e., K _d and K _oc) are not available. Furthermore, predicted leaching potential by groundwater ubiquity scores (GUS) equation was solved by using observed K _oc values and literature reported half lives of pesticides. GUS ranked the mobility of nonvolatile compounds i.e., bifenthrin, λ-cyhalothrin, cypermethrin and endosulfan extremely low; methyl parathion very low; 4-nitrophenol low; carbofuran and monocrotophos very high in S.C.L and S.L soils, respectively. Results discussed in this paper provide background to prioritize pesticides or chemical groups that should be evaluated under field conditions with regard to their leaching potential to groundwater in arid climates.     

Relationships between octan‐1‐ol/water partition coefficients,aqueous activity coefficients and reversed phase HPLC capacity factors of alkylbenzenes,chlorobenzenes, chloronaphthalenes and chlorobiphenyls

Linear relationships between logarithms of octan‐1‐ol/water partition coefficients (K_d,oct), aqueous activity coefficients (y_aq) and extrapolated RP HPLC capacity factors (k‘_w) are found for four types of aromatic hydrocarbons (alkylbenzenes and poly‐chlorinated benzenes, ‐naphthalenes and ‐biphenyls).

Both log K,_d,oct and logk‘_w increase with the increasing number of chlorine or methyl‐ene substituents. These increases of log K,_d,oct and log k‘_w are proportional and almost independent of the parent compound. In addition, these increases are linear to increases of logy_aq. The slopes of logk‘_w‐logy_aq and log K,_d,oct‐logv_aq relationships deviate significantly from 1.0. This suggests that the activity coefficients of the test compounds in both octan‐1‐ol and in the stationary phase of the RP column increase after substitution of aromatic compounds with methylene or chlorine.     

Adsorption and movement of carbaryl in soils: A verification of cosolvent theory and comparison of batch equilibrium and soil thin layer chromatography results

Batch equilibrium and soil thin layer chromatography (TLC) techniques were used to investigate the influence of different volume fractions of organic cosolvents (acetone and methanol) on the adsorption and movement of carbaryl in four different types of Indian soils. L-shaped isotherms were obtained for both the cosolvent–water mixtures at all f _s values and were in close agreement with the Freundlich equation. Higher adsorption was observed on F.R.I. soil (FSL) followed by Alampur soil (ASL), Kalai soil (KL), and Bhoran soil (BSL) at all f _s values for both the cosolvent systems as was anticipated from the K and K _D values. The K and K _D values also confirmed that carbaryl adsorption was higher in methanol–water mixture than acetone–water mixture and decreased with increasing f _s values. The frontal R _f values obtained from soil TLC studies were inversely proportional to the K and K _D values for both the cosolvent systems. The higher K and K _D values and lower R _f values in methanol–water mixtures relative to acetone–water mixtures for all the soils indicated that acetone had a greater potential for ground water contamination compared to methanol. The adsorption data were used to evaluate the cosolvent theory for describing adsorption of carbaryl in acetone–water and methanol–water mixtures. The aqueous phase partition coefficients, K _DW (mol g^?1), normalized with respect to f _oc for carbaryl was evaluated by extrapolating f _s → 0.     

Kinetics of acetyl CoA: Arylamine N‐acetyltransferase from rapid and slow acetylator fish tissues

N‐acetyltransferase (NAT) activity was determined in 100 fish (Oreochromis mossambicus) livers using 2‐aminofluorene and p‐aminobenzoic acid as substrates. Overall, the liver NAT activity of the 50 females was higher than the liver NAT activity of the 50 males. The activities (mean ± SD) of NAT from kidney, blood, intestine, and liver of males was 0.42 ± 0.11, 0.12 ± 0.03, 0.12 ± 0.08, and 1.56 ± 0.54 nmol/min/mg protein for the acetylation of 2‐aminofluorene and 0.36 ± 0.09, 0.09 ± 0.01, 0.11 ± 0.04, and 0.46 ± 0.15 nmol/min/mg protein for the acetylation of p‐aminobenzoic acid. In kidney, blood, intestine, and liver from female fish, the activities obtained were 1.60 ± 0.12, 0.35 ± 0.07, 0.15 ± 0.09, and 1.89 ± 0.50 nmol/min/mg protein for 2‐aminofluorene and 0.95 ± 0.11, 0.27 ± 0.03, 0.13 ± 0.09, and 0.57 ± 0.12nmol/min/mg protein for p‐aminobenzoic acid. Kinetic constants for arylamine N‐acetyltransferase activity in kidney, blood, intestine, and liver from fish with rapid, intermediate, and slow acetylator activity were determined. Apparent K _m and V _max values for 2‐aminofluorene were 5.5 and 7‐fold higher for liver than for the other tissues. Apparent K _m and V _max values for p‐aminobenzoic acid were 3.5 and 4.7‐fold higher for liver than for the other tissues. Based on the 2‐aminofluorene NAT activity of liver, there appears to be a polymorphism in NAT activity with 16 rapid, 28 intermediate, and 56 slow acetylators among the 100 fish assayed. This is the first demonstration of acetyl CoA: arylamine N‐acetyltransferase activity in fresh water fish and could lead to the development of a fish model for monitoring the effect of pollution of water environments on native species.     

Adsorption‐desorption hysteresis of α‐endosulfan in tropical soils using isotopic techniques

This study was designed to evaluate the adsorption‐desorption hysteresis of endosulfan (1,2,3,4, 7,7‐hexachlorobicyclo[2,2,1]‐2‐heptene‐5,6‐bisoxymethylene sulfite) in selected tropical soils. Two major tropical soils from Thailand were selected, Rangsit lowland soils (Rangsit series) and Phrabat upland soils (Pakchong series). The soil types were sub‐divided into plow soils, 0–20cm depth from the surface, and subsoils, 20–40cm depth. Adsorption was determined in 24h batch equilibrium, with five different concentrations of ¹⁴C endosulfan ranging from 1.04 to 16.64 ng/mg soils. Four successive desorption studies were performed continuously after three adsorption concentrations, 24h for each successive. Adsorption coefficient values (K _ads) as determined by Freundlich model ranged from 0.02 to 0.14 and found to be higher in Rangsit soils as expected when compared with Phrabat soils. Desorption was hysteresis in every desorption study. Desorption coefficient values (K _des) were higher than adsorption (K _des).     

Struktur-Aktivitätsbeziehungen (QSAR)

The correlation between the bioconcentration (BCF) of 20 pesticides and 3 PCB-congeners from two test soils in earthworms (Lumbricus terrestris) and the corresponding log K_ow was investigated. The relationship, expressed by the equation log BCF=a· log K_ow+b, did not show strong statistical correlation, especially for the soil with higher organic matter content. However, strong statistical correlation could be demonstrated between log BCF and log K_ow for both soils when the bioconcentration in earthworms was calculated on the basis of interstitial water instead of soil. The resulting equations represent a useful tool for assessing the bioaccumulation potential of organic chemical in soil.     

几类有机污染物的微塑料/水分配系数的线性溶解能关系模型

水体中的微塑料会吸附其中的有机污染物,影响有机污染物和微塑料的环境归趋和生态毒性。研究微塑料对有机污染物的吸附行为,对于评价有机污染物和微塑料的环境赋存、迁移及生物有效性有重要意义。污染物在微塑料与水之间的平衡分配系数(Kd),是表征微塑料对有机污染物吸附能力的重要参数。实验方法难以逐个测定众多有机污染物的Kd值,有必要发展其预测模型。本研究搜集了有机污染物的线性溶解能关系(LSER)参数及Kd值,构建了可预测有机污染物在聚丙烯微塑料与海水、聚乙烯微塑料与海水、聚乙烯微塑料与淡水之间Kd值的LSER模型。模型具有良好的拟合优度(R2adj介于0.794~0.903)、稳健性(Q2LOO和Q2BOOT分别介于0.763~0.863和0.720~0.804)和预测能力(R2ext和Q2ext分别介于0.886~0.971和0.825~0.954),能够用于预测多氯联苯、多环芳烃、六氯环已烷和氯苯类有机污染物的Kd值。     

Paeonol promotes arylamine N‐acetyltransferase activity in human bladder tumor cells

Paeonol was used to determine effects of arylamine N‐acetyltransferase (NAT) activity in human bladder tumor cells. The NAT activity was measured by high performance liquid chromatography assaying for the amounts of N‐acetyl‐2‐aminofluorene (2‐AAF) and N‐acetyl‐p‐amino‐benzoic acid (N‐Ac‐PABA) and remaining 2‐aminofluorene (2‐AF) and p‐aminobenzoic acid (PABA). The NAT activity in human bladder tumor cells was promoted by paeonol in a dose‐dependent manner, i.e. the higher the concentration of paeonol, the higher the promotion of NAT activity. The data also indicated that paeonol increases the apparent values of K_m and K_max from human bladder tumor cells in cytosols and intact cells. This report is the first demonstration to show paeonol did promote human bladder tumor cell NAT activity.     

Biokonzentration von persistenten superlipophilen Chemikalien in aquatischen Organismen

According to generally accepted theory, persistent superlipophilic chemicals with logn-octanol/water partitioning coefficient (log K_ow) >6 and molecular sizes >9,5 Å, such as octachlorodibenzo-p-dioxin, decachlorobiphenyl, Mirex etc., do not significantly bioconcentrate in aquatic organisms from ambient water. In the light of new results and considerations, this hypothesis has to be revised. The most convincing argument against this hypothesis is that in all bioconcentration experiments with superlipophilic chemicals compound concentrations have been applied which exceeded water solubility by several orders of magnitude. In this paper we describe various methods how to determine bioconcentration (BCF) factors of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin and Mirex, BCF values evaluated by this means match well those calculated by QSARs for fish and mussels based on log K_ow and water solubility as well. As expected these BCF values exceed previous ones by several orders of magnitude. As practical consequences, we recommend for BCF evaluations of superlipophilic chemicals:

1. flow-through systems, kinetic method (OECD guideline No 305 E)
2. ambient concentrations≤water solubility.

*** DIRECT SUPPORT *** A00HP013 00002     

Cleanup by solid‐phase extraction and HPLC of organochlorine insecticides and PCBS in various nonfatty and fatty samples

An accurate, simple and cheap extraction and cleanup procedure for capillary GC analysis of organo‐chlorine insecticides (OCs) in vegetables (cabbage and carrots) at the ng/g level, and for soil at the μg/g level is presented. The cleanup is carried out on solid‐phase extraction (SPE) cartridges, filled with 500 mg silica, 1 g of deactivated Florisil (10% w/w water), and 100 mg of anhydrous sodium sulphate. Recoveries >90% are obtained. The cleanup of OCs in fatty samples on an HPLC LiChrosorb Si 100 column is evaluated for subsequent capillary GC analysis. Fractionation of OCs and Aroclor 1254 and 1260 on an HPLC Nucleosil 100 column appears to be satisfactory.     

The acidobasic and complexation properties of Humic acids

Complexation of Humic Acids (HA) of different origin, like Fluka, and especially those extracted from bohemian brown coal, with cadmium(II) and lead(II) was studied at pH 5.0 using differential pulse anodic stripping voltammetry. Conditions close to those present in the environment were chosen with 3‐ 10^‐4 moll^‐4 for HAs and 2. 10^‐8‐l . 10^‐5 moll^‐1 for Cd(II) and Pb(II). Stability constants evaluation was done assuming the electrode process is diffusion controlled and the complexes are labile. Obtained log K values were in the range 4.49–5.25 for Cd(II) and as expected the higher log K values 6.05–6.60 were found for Pb(II). There was no significant difference between complexation properties of HA extracted from bohemian brown coal and that of Fluka. The results obtained are in good agreement with the literature and those obtained by ISE in our laboratory.     

Clam‐sediment accumulation factors for polychlorinated biphenyl congeners at a contaminated estuarine marsh

Clam‐sediment accumulation factors for hexa‐, hepta‐ and octa‐chlorobiphenyls were estimated at an intertidal marsh that has been contaminated with Aroclor 1268. Accumulation factors for PCB congeners with K _ow > 6.5 were in the range of 0.07–0.88, indicating that their uptake was hindered by steric factors, contamination levels, non‐equilibrium conditions and stronger affinity to sediment organic carbon. Biota‐sediment accumulation factors (BSAFs) were negatively correlated with log K _ow of superhydrophobic PCB congeners. BSAFs estimated based on 2,3,7,8‐TCDD equivalents of PCBs were 2‐fold greater than those derived from total PCB concentrations.     

Spatial distribution of perfluorooctane sulfonate (PFOS) in major rivers in southwest Nigeria

Concentrations of perfluorooctane sulfonate (PFOS) were measured for the first time in major rivers within southwest, Nigeria. PFOS was concentrated from water and sediment using solid-phase extraction, identified and quantified with high-performance liquid chromatography coupled with tandem mass spectrometry. Concentrations of PFOS ranged from 1.71 to 16.19 ng L^?1 in water, and from 1.64 to 10.29 ng g^?1 in sediments across all locations. Comparatively, the concentrations of PFOS observed in this study were within the range ever measured in the environment. Field-based sediment water distribution coefficients (log K_d, L kg^?1) ranged from 2.08 to 3.56. While no correlation was observed between K_d and organic carbon contents, there was significant positive correlation between K_d and salinity (r² = 0.7867), which suggested that activities capable of increasing salinity can enhance PFOS removal from the environment.     

Organochlorine insecticide residues in Egyptian mothers’ milk

Two hundred ninety‐two mother's milk samples were collected during 1994 from ten Egyptian governorates representing rural, metropolitan, and newly reclaimed desert areas. The samples were analyzed for 14 organochlorine insecticides and metabolites using electron capture gas chromatography and confirmed by gas chromatography/mass spectrometry (GC/MS). The overall samples average showed that the most abundant organochlorine insecticide residues were p,p'‐DDE, α‐endosulfan, β‐HCH and, p,p’‐DDT. Residues in the range of not detectable to less than 14μg/l whole milk were recorded for α‐HCH, heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin endrin aldehyde and p,p'‐DDD. The percentage of samples exceeding the acceptable daily intake for children (ADIs) set by the FAO/WHO ranged from 19% to 44% in all governorates included in the study except the governorate of Minia in which only 2.6% of the samples exceeded the ADI values. The insecticides exceeding ADI values are mostly heptachlor and heptaclor epoxide (ADI = 3.12 μg/1 whole milk).     

Uptake and transformation of perchlorate by vascular plants

Phytoremediation is a promising new method that uses green plants to cleanse soil and water contaminated with organic or inorganic pollutants. In this study, the uptake and transformation of sodium perchlorate (NaClO₄) using four vascular plant species were examined in batch experiments. The species include two trees, cabbage gum (Eucalyptus amplifolia) and eastern cottonwood (Populus deltoides), a herbaceous wetland plant, perennial glasswort (Salicornia virginica), and a herbaceous aquatic plant, waterweed (Elodea canadensis). Perchlorate was depleted from solution in the presence of all but one species (waterweed). Depletion was calculated as a first‐order kinetics reaction with k values in the range of 0–0.013 per day and accumulation of perchlorate was between 3.2 and 3138 mg/kg. Perchlorate and transformation metabolites (chlorate, chlorite, chloride) were observed in all plant tissues (e.g., roots, stems, leaves) analyzed. Results suggest that significant influences on perchlorate uptake include: (1) plant species present, (2) concentration of perchlorate, (3) sand versus hydroponic treatments, (4) the presence or absence of plant nutrients or competing ions, (5) stage of plant maturity.     

pH dependence of copper adsorption in vineyard soils of Geneva

Copper adsorption by vineyard soils of the Geneva canton was evaluated by batch equilibration experiments in a pH range from 4 to 6. The adsorption curves fit significantly to Freundlich function log q = n log C + log K_f, where q is adsorbed Cu concentration on the solid phase and C is solution Cu concentration at the end of the equilibration time. Moreover, we found that Freundlich parameters n and log K_f are moderately correlated to pH, yielding the following equations: log K_f = 0.23 pH + 0.51 (R ² 0.59) and n = –0.12 pH + 1.06 (R ² 0.59). Such equations may be useful to predict Cu mobility for risk assessment studies.     

农药类化合物对大型溞的毒性作用模式:与基线毒性化合物比较研究

农药在控制有害生物的同时,对水生生态系统产生较大的毒性效应。本文通过实验获得了25种基线化合物对大型溞的急性毒性数据,并与57种农药类化合物对大型溞的急性毒性数据进行比较研究,同时根据体外浓度LC_(50)、生物富集因子BCF和体内临界浓度CBR的关系,计算了这些化合物在大型溞体内的临界浓度,研究了农药类化合物对大型溞的毒性作用机理。结果表明,基线化合物在大型溞体内的临界浓度log1/CBR值在一个很窄的范围波动,而农药类化合物在大型溞体内的临界浓度log1/CBR值范围广且较高。这说明多数农药类化合物对大型溞为反应性毒性作用模式。其中,除草剂对大型溞的毒性显著低于杀菌剂和杀虫剂对大型溞的毒性。这可能是因为除草剂主要通过干扰植物光合作用、植物激素或植物分子合成发挥毒性效应,从而导致其对大型溞的生理系统难以发生反应性毒性效应。而杀虫剂和杀菌剂主要通过干扰生物神经系统、生殖系统、呼吸作用或大分子合成发挥毒性效应,因此易与大型溞生理系统发生生物化学反应,从而具有较高的毒性效应。本文分别建立了除草剂、杀菌剂和杀虫剂对大型溞的急性毒性QSAR模型。除草剂对大型溞的急性毒性机理较简单,其毒性与化合物疏水性程度和离子化程度有关;而杀菌剂对大型溞的急性毒性主要与化合物的标准生成热和极性表面积有关;杀虫剂对大型溞的急性毒性作用机理较复杂,它们对大型溞的毒性效应与其和生物分子之间的氢键和范德华力有关。     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.