Applicability of microwave-assisted extraction combined with LC-MS/MS in the evaluation of booster biocide levels in harbour sediments

A new sample treatment method for the determination of four common booster biocides (Diuron, TCMTB, Irgarol 1051 and Dichlofluanid) in harbour sediment samples has been developed that uses liquid chromatography-tandem mass spectrometry (LC-MS/MS) after microwave-assisted extraction, followed by clean-up and a solid phase extraction preconcentration step (MAE-SPE). The effects of different variables on MAE-SPE were studied. The recoveries obtained were greater than 75%, and the relative standard deviation was less than 7%. The detection limits ranged between 0.1 and 0.3 ng g⁻¹. The developed methodology was successfully applied to the evaluation of the presence of booster biocides in sediment samples from different harbours and marinas of Gran Canaria Island (Canary Islands, Spain).     

Environmental Exposure of Aquatic and Terrestrial Biota to Triclosan and Triclocarban1

Abstract: The synthetic biocides triclosan (5‐chloro‐2‐(2,4‐dichlorophenoxy)phenol) and triclocarban (3,4,4′‐trichlorocarbanilide) are routinely added to a wide array of antimicrobial personal care products and consumer articles. Both compounds can persist in the environment and exhibit toxicity toward a number of biological receptors. Recent reports of toxicological effects in wildlife, human cell cultures, and laboratory animals have heightened the interest in the occurrence of these biocide and related toxic effects. The present study aimed to summarize published environmental concentrations of biocides and contrast them with toxicity threshold values of susceptible organisms. Environmental occurrences and toxicity threshold values span more than six orders of magnitude in concentration. The highest biocide levels, measured in the mid parts‐per‐million range, were determined to occur in aquatic sediments and in municipal biosolids destined for land application. Crustacea and algae were identified as the most sensitive species, susceptible to adverse effects from biocide exposures in the parts‐per‐trillion range. An overlap of environmental concentrations and toxicity threshold values was noted for these more sensitive organisms, suggesting potential adverse ecological effects in aquatic environments. Affirmative evidence for this is lacking, however, since studies examining environmental occurrences of biocides vis‐à‐vis the health and diversity of aquatic species have not yet been conducted.     

油气田微生物腐蚀与防护研究进展

结合笔者近年来所做的油气田微生物腐蚀领域的工作,以硫酸盐还原菌和铁氧化菌为代表性腐蚀性微生物,系统分析了油气田环境中微生物腐蚀机制及其影响因素。微生物腐蚀行为和机制与微生物的种类、材料、环境因素等密切相关,系统地统计和分析油气田腐蚀性微生物的种类和种群结构是微生物腐蚀研究基础。同时还探讨了缓蚀剂、杀菌剂及缓蚀杀菌剂在油田微生物腐蚀控制过程中存在的问题,最后针对油气田微生物腐蚀与防护研究现状,提出了一些思考和建议。     

Effect of biocides on the precipitation of calcium fluoride in the presence of anionic copolymeric inhibitors

The inhibitory efficiency of anionic copolymers and the effect of the biocides sodium hypochlorite, glutaraldehyde, and tris(hydroxymethyl)nitromethane on the precipitation behavior of calcium fluoride (CaF₂) were studied. The efficiency of polymeric inhibitors was traced from conductivity measurements by using half-life (t_1/2) method. X-ray diffraction parameters have been measured for calcium fluoride scale minerals. An anionic copolymer (K-798) acts as one of the best inhibitors for the precipitation process of the calcium fluoride in water as compared to K-775. It is assigned to the fact that the copolymer (K-798) contains both sulfonic acid and sulfonated styrene groups while the polymer (K-775) having only the sulfonic acid group. It was further observed that the biocides have no appreciable effect on the performance of the anionic polymeric inhibitors.     

Comparative toxicities of 10 widely used biocides in three freshwater invertebrate species

Owing to their widespread use in wooden products, industrial products, cosmetics, and personal care products, biocides are frequently detected in wastewater and surface water. In this study, I examined the acute toxicities of 10 commonly used biocides, namely methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, iodopropynyl butylcarbamate, triclosan, azoxystrobin, pyraclostrobin, climbazole, and clotrimazole, in the water flea (Daphnia similis), freshwater planarians (Dugesia japonica) and green neon shrimp (Neocaridina denticulata). Among the 10 tested biocides, dichlorooctylisothiazolinone was the most toxic to both D. similis and N. denticulata, whereas pracolstrobin was the most toxic to Du. japonica. By contrast, the least toxic biocides for D. similis, Du. japonica, and N. denticulata were climbazole, iodopropynyl butylcarbamate, and methylisothiazolinone, respectively. The 48-h nominal LC₅₀ values of all the biocides, except for benzisothiazolinone and climbazole, in D. similis were mostly less than 1 mg/L. In addition, the 96-h nominal LC₅₀ values of all the biocides, except for methylisothiazolinone and iodopropynyl butylcarbamate, in Du. japonica was less than 1 mg/L. These results indicate the biocides with low LC₅₀ values are relatively toxic to freshwater organisms.     

一种新型高效复合溴基杀菌剂的研制及应用

介绍了溴类杀生剂的优势及国内外发展状况，溴基杀生剂DBNPA的实验室合成，工业放大以及现场应用效果等情况。     

异噻唑啉酮类杀菌剂对黑斑蛙胚胎和蝌蚪的急性毒性

异噻唑啉酮类杀菌剂1,2-苯并异噻唑-3-酮(BIT)和甲基异噻唑啉酮(MIT)虽已在多种行业中广泛使用,但目前有关其毒性尤其对水体中生物毒性的数据还较少。鉴于BIT和MIT在水体中普遍存在,本文研究了这两种污染物对两栖动物黑斑蛙胚胎和蝌蚪的急性毒性。黑斑蛙胚胎和蝌蚪分别暴露系列浓度的BIT和MIT,观察化学品对其生长、发育和运动的影响,计算96小时半数致死浓度(96 h-LC50)和96小时半数致畸浓度(96 h-TC50),确定最小生长抑制浓度(MCIG)。结果发现,BIT对黑斑蛙胚胎的96 h-LC50和96 h-TC50分别为2.99 mg·L-1和0.60 mg·L-1,MCIG小于0.40 mg·L-1,对蝌蚪的96 h-LC50为6.44 mg·L-1。MIT对黑斑蛙胚胎的96 h-LC50和96 h-TC50分别为5.30 mg·L-1和2.36 mg·L-1,MCIG为2.59 mg·L-1,对蝌蚪的96 h-LC50为7.58 mg·L-1。根据《化学农药环境安全评价准则报批稿》中两栖动物蝌蚪急性毒性的分级标准,判定BIT和MIT的毒性等级为中等。该毒性数据可为异噻唑啉酮类杀菌剂的环境管理提供参考。     

Determination of optimal water solubility of capsaicin for its usage as a non-toxic antifoulant

BACKGROUND: Capsaicin, a non-toxic natural product antifoulant, is an attractive alternative to the currently used toxic metal-based antifoulants for protecting the submerged surfaces. The problem associated with conducting capsaicin experiments is its limited aqueous solubility. METHODS: A procedure was developed to obtain the maximum capsaicin concentration in water. Capsaicin was first dissolved in one of the three organic solvents, methanol, ethanol, and acetone. The organic solvent was replaced by gradually adding distilled water and evaporating the organic solvent. RESULTS: The best solvent for obtaining highest concentration of capsaicin in water was ethanol. A maximum capsaicin in water 6400 ppm was achieved by using 16 mg capsaicin dissolved in 0.8 ml ethanol followed with the addition of 2.5 ml distilled water in 0.2 ml increments and then slow evaporation of the solvent. CONCLUSION: The concentration obtained using our approach is well above the threshold concentration of capsaicin in deterring the marine organism attachments.     

Occurrence of imidacloprid,carbendazim, and other biocides in Italian house dust: Potential relevance for intakes in children and pets

The occurrence of pesticides intended for non-agricultural use was investigated in 206 dust samples drawn from vacuum-cleaner bags from residential flats in Italy. The multi-residue analysis targeted on 95 different active principles was performed with UPLC-MS/MS, with a Limit of Quantification (LOQ) of 0.008 μg/g dry weight. The results indicated the presence of imidacloprid (IMI) and carbendazim (CARB) in 30% and 26% of the samples, with a mean and P95 concentration between 1.6 and 39 and between 0.08 and 4.9 μg/g, respectively. Combined presence of two biocides was noted in 19.4% samples, of three biocides in 9.2% samples, of four biocides in 3.4% samples, and of five and six biocides in 0.5% and 1% samples, respectively. According to the estimated dust intake in infants/toddlers aged 6–24 months (16–100 mg d^?1) and cats (200 mg d^?1), it was possible to obtain risk characterization with respect to the Acceptable Daily Intake (ADI) for IMI of 0.060 mg/kg body weight (bw) proposed by the European Food Safety Authority (EFSA) and the chronic Population Adjusted Dose (cPAD) of 0.019 mg/kg bw d^?1 by US-EPA. Under the worst-case scenario, the presence of IMI in dust indicates potential exceedance of the cPAD in kittens, to be considered as sentinel also accounting for combined exposure. This study highlights the relevance of consumer empowerment about the responsible use of pesticides as biocidal products in indoor environment.     

Degradation of a commercial textile biocide with advanced oxidation processes and ozone

The occurrence of significant amounts of biocidal finishing agents in the environment as a consequence of intensive textile finishing activities has become a subject of major public health concern and scientific interest only recently. In the present study, the treatment efficiency of selected, well-known advanced oxidation processes (Fenton, Photo-Fenton, TiO(2)/UV-A, TiO(2)/UV-A/H(2)O(2)) and ozone was compared for the degradation and detoxification of a commercial textile biocide formulation containing a 2,4,4'-trichloro-2'-hydroxydiphenyl ether as the active ingredient. The aqueous biocide solution was prepared to mimic typical effluent originating from the antimicrobial finishing operation (BOD(5,o) < or =5 mg/L; COD(o)=200 mg/L; DOC(o) (dissolved organic carbon)=58 mg/L; AOX(o) (adsorbable organic halogens)=48 mg/L; LC(50,o) (lethal concentration causing 50% death or immobilization in Daphnia magna)=8% v/v). Ozonation experiments were conducted at different ozone doses (500-900 mg/h) and initial pH (7-12) to assess the effect of ozonation on degradation (COD, DOC removal), dearomatization (UV(280) and UV(254) abatement), dechlorination (AOX removal) and detoxification (changes in LC(50)). For the Fenton experiments, the effect of varying ferrous iron catalyst concentrations and UV-A light irradiation (the Photo-Fenton process) was examined. In the heterogenous photocatalytic experiments, Degussa P25-type TiO(2) was used as the catalyst and the effect of reaction pH (3, 7 and 12) and H(2)O(2) addition on the photocatalytic treatment efficiency was examined. Although in the photochemical (i.e. Photo-Fenton, TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)) experiments appreciably higher COD and DOC removal efficiencies were obtained, ozonation appeared to be equally effective to achieve dearomatization (UV(280) abatement) at all studied reaction pH. During ozonation of the textile biocide effluent, AOX abatement proceeded significantly faster than dearomatization and was complete after 20 min ozonation (267 mg O(3)). On the other hand, for complete detoxification, ozonation had to be continued for at least 30 min (corresponding to 400mg O(3)). Effective AOX and acute toxicity removal was also obtained after heterogeneous photocatalytic treatment (TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)). The Fenton-based treatment experiments and particularly the dark Fenton reaction resulted in relatively poor degradation, dearomatization, AOX and acute toxicity removals.