Systematic review on skin adverse effects of important hazardous hair cosmetic ingredients with a focus on hairdressers.

BACKGROUND: The burden of occupational hand eczema in hairdressers is high, and (partly strong) allergens abound in the hair cosmetic products they use. OBJECTIVES: To systematically review published evidence concerning contact allergy to an indicative list of active ingredients of hair cosmetics, namely, p-phenylenediamine (PPD), toluene-2,5-diamine (PTD), persulfates, mostly ammonium persulfate (APS), glyceryl thioglycolate (GMTG), and ammonium thioglycolate (ATG), concerning the prevalence of sensitization, particularly in terms of a comparison (relative risk; RR) between hairdressers and non-hairdressers. METHODS: Following a PROSPERO-registered and published protocol, eligible literature published from 2000 to February 2021 was identified, yielding 322 publications, and extracted in standardized publication record forms, also considering risk of bias. RESULTS: Based on 141 publications, the contact allergy prevalence to PPD was 4.3% (95% CI: 3.8-4.9%) in consecutively patch tested patients. Other ingredients were mostly tested in an aimed fashion, yielding variable, and partly high contact allergy prevalences. Where possible, the RR was calculated, yielding an average increased sensitization risk in hairdressers of between 5.4 (PPD) and 3.4 (ATG). Additional evidence related to immediate-type hypersensitivity, experimental results, exposures, and information from case reports was qualitatively synthesized. CONCLUSIONS: An excess risk of contact allergy is clearly evident from the pooled published evidence from the last 20 years. This should prompt an improvement in working conditions and product safety.

Association of hairdressing with cancer and reproductive diseases: A systematic review.

OBJECTIVES: To review recent epidemiological studies investigating carcinogenic or reprotoxic effects among hairdressers who seem to be at greater risk for systemic adverse effects of chemicals released from hair care products than consumers. METHODS: A systematic review according to the PRISMA-P guidelines was performed and included studies published from 2000 to August 2021, in which cancer or adverse reproductive effects were diagnosed in 1995 and onward. Data were synthetized qualitatively due to the small number of studies, heterogeneity of study designs, outcomes, and methods. RESULTS: Four studies investigating cancer frequencies and six studies investigating effects on reproduction among hairdressers were identified. All were of good quality and with low risk of bias. Only one of the four studies found an increased risk of cancer reporting nine times higher odds for bladder cancer in hairdressers than the population-based controls. Three other studies investigating bladder and lung cancer, and non-Hodgins lymphoma did not find an increased risk in hairdressers. Regarding reprotoxic effects, numerous outcomes were investigated including menstrual disorders, congenital malformations, fetal loss, small-for-gestational age newborns, preterm delivery, and infertility. Increased risk was found for ventricular septal defect in newborns of fathers working as hairdressers. Furthermore, several indices of poor neonatal or maternal health were significantly associated with mothers working as hairdresser. CONCLUSIONS: Despite the scarce evidence that hairdressers are at increased risk of carcinogenic or reprotoxic effects related to their trade, such health risks cannot be ruled out. Therefore, preventive efforts to diminish occupational exposures to hairdressing chemicals should be targeted.

Skin Toxicity of Selected Hair Cosmetic Ingredients: A Review Focusing on Hairdressers.

The safety assessment of cosmetics considers the exposure of a 'common consumer', not the occupational exposure of hairdressers. This review aims to compile and appraise evidence regarding the skin toxicity of cysteamine hydrochloride (cysteamine HCl; CAS no. 156-57-0), polyvinylpyrrolidone (PVP; CAS no. 9003-39-8), PVP copolymers (CAS no. 28211-18-9), sodium laureth sulfate (SLES; CAS no. 9004-82-4), cocamide diethanolamine (cocamide DEA; CAS no. 68603-42-9), and cocamidopropyl betaine (CAPB; CAS no. 61789-40-0). A total of 298 articles were identified, of which 70 were included. Meta-analysis revealed that hairdressers have a 1.7-fold increased risk of developing a contact allergy to CAPB compared to controls who are not hairdressers. Hairdressers might have a higher risk of acquiring quantum sensitization against cysteamine HCl compared to a consumer because of their job responsibilities. Regarding cocamide DEA, the irritant potential of this surfactant should not be overlooked. Original articles for PVP, PVP copolymers, and SLES are lacking. This systematic review indicates that the current standards do not effectively address the occupational risks associated with hairdressers' usage of hair cosmetics. The considerable irritant and/or allergenic potential of substances used in hair cosmetics should prompt a reassessment of current risk assessment practices.

Occupational Exposure of Hairdressers to Airborne Hazardous Chemicals: A Scoping Review.

INTRODUCTION: Exposure to hazardous chemicals released during hairdressing activities from hair care products puts hairdressers at risk of adverse health effects. Safety assessments of hair products are mainly focused on consumers, but exposure for professional hairdressers might be substantially higher. OBJECTIVE: To identify and assess available research data on inhalation exposures of professional hairdressers. METHODS: A systematic search of studies between 1 January 2000 and 30 April 2021 was performed in Medline, Embase, Web of Science and in Cochrane registry, toxicological dossiers of the Scientific Committee on Consumer Safety (SCCS) of the European Commission as well as the German MAK Commission. Studies reporting quantitative data on airborne concentrations of chemicals in the hairdresser's workplace were considered. The outcome was an airborne concentration of chemicals in the working environment, which was compared, when possible, with current occupational exposure limits (OEL) or guidance levels. RESULTS: In total, 23 studies performed in 14 countries were included. The average number of hairdressing salons per study was 22 (range 1-62). Chemicals most frequently measured were formaldehyde (n = 8), ammonia (n = 5), total volatile organic compounds (TVOC) (n = 5), and toluene (n = 4). More than fifty other chemicals were measured in one to three studies, including various aromatic and aliphatic organic solvents, hydrogen peroxide, persulfate, and particulate matter. Most studies reported environmental air concentrations, while personal exposure was measured only in seven studies. The measured air concentrations of formaldehyde, ammonia, and TVOC exceeded OEL or guidance values in some studies. There was large variability in measuring conditions and reported air concentrations differed strongly within and between studies. CONCLUSION: Hairdressers are exposed to a wide spectrum of hazardous chemicals, often simultaneously. Airborne concentrations of pollutants depend on salon characteristics such as ventilation and the number of customers but also on used products that are often country- or client-specific. For exposure to formaldehyde, ammonia, and TVOC exceeding OELs or guidance values for indoor air was observed. Therefore, occupational exposure should be taken into account by safety regulations for hair care products.

Respiratory toxicity of persulphate salts and their adverse effects on airways in hairdressers: a systematic review.

OBJECTIVE: To review the literature on respiratory effects of persulfate salts (PS) or hair bleaches in hairdressers and animal models exploring mechanisms behind PS-induced asthma. METHODS: A systematic review according to the PRISMA guidelines was performed. Studies published from 2000 to July 2021 that fulfilled predefined eligibility criteria were retrieved. Data were not quantitatively synthesized due to the heterogeneity of study designs, outcomes and methods. RESULTS: Forty-two articles were included. PS are indicated as the main cause of occupational rhinitis and asthma in hairdressers, and one of the leading causes of occupational asthma in some European countries. Bleaching products are indicated as the most important factor for development of respiratory symptoms, lung function decline, and leaving the hairdressing profession. Risk estimates from a good quality prospective study showed up to 3.9 times higher risk for wheezing and breathlessness in hairdressers aged ≥ 40 years than in matched controls, and 20 times higher risk in hairdressers to develop respiratory symptoms from exposure to bleaching powder than controls. Pathophysiological mechanisms of the respiratory response to PS are not yet fully elucidated, but may include non-specific and specific immune responses. CONCLUSIONS: Hairdressing is associated with a wide spectrum of respiratory adverse effects, of which bleaching products were indicated as the most hazardous. Preventive measures for reducing inhalatory exposure to PS in hair salons should be re-evaluated, including adopting occupational exposure limits at EU level, and encouraging use of safer bleach formulations. PROSPERO REGISTRATION NUMBER: CRD42021238118.

Prevalence and incidence of hand eczema in hairdressers-A systematic review and meta-analysis of the published literature from 2000-2021.

BACKGROUND: Hairdressers are commonly affected by hand eczema (HE) due to skin hazardous exposure such as irritants and allergens in the work environment. OBJECTIVE: To give an overview of the current prevalence, incidence, and severity, as well as the pattern of debut and the contribution of atopic dermatitis on HE in hairdressers. METHODS: A systematic review according to the Preferred Reporting Items for Systematic Reviews and Meta-Analysis (PRISMA) guidelines was performed. Studies published from 2000 to April 2021 that fulfilled predefined eligibility criteria were retrieved. RESULTS: A pooled lifetime prevalence of 38.2% (95% confidence interval [CI] 32.6-43.8), a pooled 1-year prevalence of 20.3% (95% CI 18.0-22.6), and a pooled point prevalence of 7.7% (95% CI 5.8-9.6) of HE was observed in hairdressers. The lifetime prevalence in fully trained hairdressers and hairdressing apprentices was almost identical. The pooled incidence rate of HE was 51.8 cases/1000 person-years (95% CI 42.6-61.0) and the pooled prevalence of atopic dermatitis was 18.1% (95% CI 13.6-22.5). CONCLUSION: HE is common in hairdressers and most hairdressers have debut during apprenticeship. The prevalence of atopic dermatitis in hairdressers is comparable with estimates in the general population, indicating that occupational exposures are the main factor in the increased prevalence of HE in hairdressers. This warrants a strategic and collective effort to prevent HE in hairdressers.

Allergic contact dermatitis caused by 2-hydroxyethyl methacrylate and ethyl cyanoacrylate contained in cosmetic glues among hairdressers and beauticians who perform nail treatments and eyelash extension as well as hair extension applications: A systematic review.

Current cosmetic regulations primarily focus on protecting consumers, not the professional user who is subjected to a partly different, and certainly more intense exposure to hazardous substances. Against this background, this systematic review aims to compile and appraise evidence regarding skin toxicity of 2-hydroxyethyl methacrylate (HEMA; CAS no. 212-782-2) and ethyl cyanoacrylate (ECA; CAS no. 7085-85-0) contained in cosmetic glues used among hairdressers and beauticians who perform nail treatments and eyelash extension as well as hair extension applications. This systematic review followed the Preferred Reporting Items for Systematic review and Meta-Analysis (PRISMA) 2020 recommendations for reporting systematic reviews and meta-analysis. In total, six publications from six countries were eligible for this systematic review. A meta-analysis revealed that hairdressers and beauticians have a ninefold increased risk of developing contact allergy to HEMA compared with controls who are not hairdressers and beauticians. Results for ECA are lacking. The results of this systematic review clearly show that-regarding contact allergy to acrylates-it is not appropriate to apply risk assessment for consumers to hairdressers and beauticians who occupationally handle cosmetic glues. The regulations in existence do not adequately address occupational risks for hairdressers and beauticians connected with the use of acrylate-containing cosmetic substances and need reconsideration.

Differences between hairdressers and consumers in skin exposure to hair cosmetic products: A review.

Hairdressers are at high risk of developing occupational hand eczema. Opinions on the health and safety concerns of nonfood consumer products, such as cosmetics and their ingredients, consider the exposure of a "common consumer," which may not account for occupational exposure of hairdressers. As a result, there is a parlous scenario in which serious safety concerns about occupational exposures are present. The purpose of this review is to compare the frequency of exposure to various types of hair cosmetic products among hairdressers and consumers. Database searches for this review yielded a total of 229 articles; 7 publications were ultimately included. The analysis showed that-dependent on the task-hairdressers were exposed 4 to 78 times more than consumers to a wide spectrum of hair cosmetic products used in their daily working life, ranging from shampoos, conditioners, oxidative and nonoxidative hair colors, to bleaching agents. The highest frequency was found for coloring hair with oxidative hair color. Consumer use frequency does not appear to be appropriate for representing hairdresser exposure. The current standards do not effectively address the occupational risks associated with hairdressers' use of cosmetics. The findings of this study should cause current risk-assessment procedures to be reconsidered.

Key molecules in the GABA signalling pathway are present in mouse and human cervical tissue.

Cervical mucus modulates fertility by cyclical changes of its biophysical and functional properties. Based on an analogy with bronchial goblet cells we set out to investigate the possible role of the gamma-aminobutyric acid (GABA) signalling pathway in the mediation of oestrogen-induced mucus secretion from endocervical secretory cells. The aim of the study was to examine the existence of GABAA receptor (GABAAR), glutamic acid decarboxylase 65/67 (GAD65/67) and vesicular GABA transporter (VGAT) in human and mouse cervical tissue. The mouse cervical tissue expressed GabaAR mRNA transcripts throughout the oestrous cycle. GABAAR-positive immunolabelling was present in the superficial layer of the mouse cervico-vaginal epithelium in pro-oestrus. Human cervical tissue showed the presence of GABAAR, GAD67 and VGAT mRNA transcripts and clear immunofluorescent signals of all three molecules were detected in the endocervical secretory epithelium. The results of this study confirmed that elements of the GABA signalling pathway are present in the secretory epithelium of mouse and human cervical tissue and that GABA signalling pathway could be considered a possible mediator in oestrogen regulation of mucus secretion in the endocervical glands.

Multi-class determination of pharmaceuticals in wastewaters by solid-phase extraction and liquid chromatography tandem mass spectrometry with matrix effect study.

In this work, a multi-class analytical method for determination of 22 frequently used pharmaceuticals was developed and validated. Analytes were from different classes for example macrolides, fluoroquinolones, tetracyclines, sulfonamides, anthelmintics, anesthetics, and others. Method was intended for analysis of aqueous samples so the sample preparation was done using solid-phase extraction (SPE). Different sorbents (C8, C18, polymeric, and ion exchange sorbents) combining different eluents (methanol, ethanol, acetonitrile, acetone, ethyl acetate) were investigated during development of sample preparation step. Samples were analyzed using HPLC-MS/MS, and therefore, chromatographic and mass spectrometer conditions were investigated. Optimal extraction efficiencies for most of the investigated analytes were obtained with Oasis HLB polymeric sorbents with acetonitrile as eluent. A study of matrix effect was carried out for wastewater treatment plant (WWTP) influent and effluent. The method was validated for linearity, detection limits and quantification limits, repeatability, and reproducibility. Method detection limits were in the range of 2.0-204.0 ng L-1 for WWTP influent except for sulfaguanidine and dexamethasone. Also, method detection limits for WWTP effluent were from 1.0 to 115.4 ng L-1. Method was successfully applied for analysis of real wastewater samples from municipal wastewater treatment plant. In the influent, pharmaceuticals from all investigated groups were present and the concentrations were from 50.0 to 4914.3 ng L-1 for influent and 26.9 to 1699.2 ng L-1 for effluent. It was also reported that some pharmaceuticals showed higher concentrations in the wastewater effluent than in the influent.

Effects of simvastatin on malondialdehyde level and esterase activity in plasma and tissue of normolipidemic rats.

BACKGROUND: We investigated the possible non-lipid effects of simvastatin (SIMV) on paraoxonase 1 (PON1) and butyrylcholinesterase (BuChE) activity, as well as on malondialdehyde (MDA) levels in normolipidemic rats. METHODS: Two experimental groups of Wistar rats (10mg/kg/day of SIMV) and two control groups (saline) underwent a 21-day treatment period (TP). On the 22nd day one experimental and one control group of rats were sacrificed. Remaining groups of animals were sacrificied on the 32nd day of the study (10-day after-treatment period (AT)). Blood samples and slices of liver, heart, kidney, and brain tissue were obtained for the measurement of PON1 and BuChE activity and levels of MDA. Data were analyzed by means of t-test for independent samples. p values≤0.05 were considered as statistically significant. RESULTS: SIMV caused a significant decrease of serum and liver PON1 activity (18-24%, p≤0.05) and MDA concentrations in the plasma, heart, liver, kidney, and brain (9-40%, p≤0.05), while plasma and liver BuChE activity increased by 29% (p≤0.05) and 18%, respectively. All effects of SIMV were largely diminished following AT. The exception was MDA, which remained significantly decreased in plasma and all tissues analyzed. CONCLUSION: SIMV significantly decreased PON1 activity and MDA levels and increased BuChE activity. We suggest that the decrease of MDA levels is a beneficial therapeutic effect of SIMV, for example in cardiovascular disorders, while the increase of BuChE activity, especially in brain, may be a potential adverse effect in patients with Alzheimer disease.

Analysis of anthelmintics in surface water by ultra high performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry.

A method based on ultra high performance liquid chromatography coupled to quadrupole linear ion trap mass spectrometry (UHPLC-QqLIT-MS) has been developed to investigate occurrence of 10 anthelmintic drugs from different structural groups (moxidectin, flubendazole, fenbendazole, levamisol, mebendazole, oxibendazole, albendazole, triclabendazole, febantel and praziquantel) in surface water. Analytes were pre-concentrated by solid phase extraction (SPE) using hydrophilic-lipophilic polymeric based sorbent. Quantification of investigated analytes was done using deuterated compounds as internal standards in order to minimize matrix effect. Analyte recoveries from spiked samples at two concentration levels were above 75% for most of the analytes. The main advantages of developed method are fast separation using UHPLC and therefore short analysis time, combined with good sensitivity which is demonstrated by low ngL(-1) detection limits. The developed method was applied for analysis of anthelmintics in the Llobregat River (NE Spain) and its main tributaries (rivers Anoia and Cardener). Eight out of ten anthelmintics were detected in all analyzed samples with the concentrations in low ngL(-1) level. The method fills the gap on analytical methodologies for determination of anthelmintic drugs in the environment.

The influence of gemfibrozil on malondialdehyde level and paraoxonase 1 activity in wistar and fisher rats.

There are diverse experimental data about the influence of gemfibrozil (GEM) on the production of hydrogen peroxide (H(2)O(2)) and antioxidant enzymes. We investigated the influence of GEM treatment on the production of malondialdehyde (MDA) level in tissues of normolipidaemic Wistar and Fisher rats which is an index of lipid peroxidation. Because serum paraoxonase 1 (PON1) is an important enzyme with specific protective function on metabolism of lipid peroxides, we examined the influence of GEM on PON1 activity in liver and serum. MDA level and enzyme activities were also determined 10 days after withdrawal of GEM treatment. The significantly increased levels of MDA in liver, kidney and heart of both rat strains were obtained after 3 weeks of GEM treatment. We propose two possibilities for the increase of MDA levels caused by GEM, induction of peroxisome proliferation and activities of enzymes that participated in occurrence of H(2)O(2) and possible reduction of enzyme activities including in H(2)O(2) metabolism. Ten days after withdrawal of GEM treatment, MDA levels in all tissue levels of both rat strains were less in comparison with GEM treatment. GEM caused a significant drop of PON1 activity in serum and liver of Fisher rats, and in liver of Wistar rats. We suggest that GEM, through induction of lipid peroxidation, caused the damage of hepatocytes with consequent reduction of PON1 synthesis. The increase in PON1 activity in serum and tissues of both rat strains 10 days after withdrawal of GEM treatment shows the fast recovery of enzyme synthesis.

Determination of multi-class pharmaceuticals in wastewater by liquid chromatography-tandem mass spectrometry (LC-MS-MS).

An analytical method for multi-class pharmaceuticals determination in wastewater has been developed and validated. Target compounds were: sulfonamides (sulfadiazine, sulfaguanidine, sulfamethazine, sulfamethoxazole), fluoroquinolones (ciprofloxacin, enrofloxacin, norfloxacin), diaminopyrimidine (trimethoprim), anaesthetic (procaine), anthelmintic (praziquantel and febantel), and macrolide (roxithromycin). The method involves pre-concentration and clean-up by solid-phase extraction (SPE) using Strata-X extraction cartridges at pH 4.0. Target analytes were identified and quantitatively determined by liquid chromatography-tandem mass spectrometry using multiple reaction monitoring (MRM). Recoveries were higher than 50% with relative standard deviation (RSD) below 18.3% for three concentrations. Only for sulfaguanidine was low recovery obtained. Matrix effect was evaluated using matrix-matched standards. The method detection limit (MDL) was between 0.5 and 5 ng L(-1) in spiked water samples. The precision of the method, calculated as relative standard deviation, ranged from 0.5 to 2.0% and from 1.4 to 8.3 for intra-day and inter-day analysis, respectively. The described analytical method was used for determination of pharmaceuticals in effluent wastewaters from the pharmaceutical industry.

Effects of high sucrose diet, gemfibrozil, and their combination on plasma paraoxonase 1 activity and lipid levels in rats.

We investigated the influence of high sucrose diet (HSD) after 3 or 5 weeks of administration on paraoxonase 1 (PON1) activity in plasma of normolipidemic rats and the relationship between serum PON1 activity, triacylglycerides (TGs), HDL and total cholesterol vs. the control group of rats fed normal, control diet (CD). Because the data about the influence of gemfibrozil (GEM) on PON1 activity are controversial, we also investigated its effects (administration in the 4th and 5th week in rats on HSD and CD) on plasma PON1 activity and lipid levels in normolipidemic rats, and in rats with hypertriglyceridemia caused by HSD. Our results obtained in rats on HSD show a significant increase of plasma TGs levels by 47% (P<0.05) after 5 weeks of treatment, and PON1 activity by 32% and 23% (P<0.05) after 3 and 5 weeks, but without change in lipid levels vs. rats on CD. In the rats on CD and HSD, GEM caused a significant decrease of PON1 activity by 44% and 33%, while a significant decrease of TGs level by 38% (P<0.05) was measured only in rats on CD. The effects of GEM on total cholesterol, HDL and LDL in both groups of rats were typical for its action on lipoprotein metabolism. Because GEM in the rat liver stimulates proliferation of peroxisomes, ß oxidation, and production of H2O2, it is possible that the oxidative stress induced by GEM damages hepatocytes and lowers the synthesis of PON1.

Development and optimization of the SPE procedure for determination of pharmaceuticals in water samples by HPLC-diode array detection.

This paper focuses on the investigation of different types of SPE sorbents for the preconcentration of eight veterinary pharmaceuticals from water samples. The pharmaceuticals studied were sulfamethazine, sulfadiazine, sulfaguanidine, trimethoprim, oxytetracycline, enrofloxacin, norfloxacin and penicillin G/procaine. Five different SPE materials (Strata-X, Strata-X-C, Strata SDB-L, Strata C8 and Strata C18) from Phenomenex were compared with Oasis HLB with a view to obtaining the best cartridges for all pharmaceuticals investigated. Extraction efficiency was determined by HPLC with diode array detection (DAD). HPLC-DAD separation and quantification of the selected pharmaceuticals were carried out under gradient elution by a binary mixture of 0.01 M oxalic acid and ACN based on cyano modified column (LiChrosphere 100 CN) from Merck. Strata-X provided the best results in the preconcentration of 100 mL water samples, yielding average pharmaceutical recoveries of higher than 90%, except for sulfaguanidine (76.1%). The developed Strata-X-HLPC-DAD method was validated and applied, for the efficient investigation of reverse osmosis/nanofiltration membranes and for the removal of these eight pharmaceuticals from the production wastewater samples. NF90 and XLE membranes were shown to be the best for the rejection of all investigated pharmaceuticals.

Determination of alkenes in cracking products by normal-phase high-performance liquid chromatography-diode array detection.

Alkene content determinations in fluid catalytic cracking (FCC) liquid products were performed by means of normal-phase high-performance liquid chromatography (NP-HPLC) with diode array detection (UV/DAD). Separation of alkenes from aromatic hydrocarbons was performed on amino-modified silica gel column with n-heptane as mobile phase. The column has a little affinity to alkenes and saturated hydrocarbons and a pronounced affinity to aromatic compounds. The problem of alkenes and saturates co-elution on this column type was overcome with the detection system, UV/DAD, sensitive and selective to alkenes, while saturates are inactive in UV field. Total alkene content was determined as a sum of mono- and dialkene groups quantified by external standard method. Validation and verification of the developed method proved their applicability. The following criteria were used to validate the HPLC-DAD method: selectivity, linearity, precision, limits of detection and quantification. Alkene contents were quantified with the external standard method of wide calibration range, so both low and high alkene contents can be determined by the single calibration. Correlation coefficients were higher than 0.99. Precision was evaluated as repeatability and intermediary precision with relative standard deviations less than 5%. Some structural investigation of alkene groups was performed to confirm the assumption. Proposed method was compared with certified NMR method. Six commercial motor gasoline samples were analyzed by these two methods. Obtained results indicate good agreement between alkene content determined by both methods. The developed method was applied to the determination of alkene content in liquid FCC products in the boiling range from 70 degrees C to 190 degrees C.

Influence of suspended clay minerals and humic matter on the solid phase extraction efficiency of selected pesticides from water.

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and alpha-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was > or =0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.