Formation of dioxins during exposure of pesticide formulations to sunlight

Holt, Eva; Weber, Roland; Stevenson, Gavin; Gaus, Caroline

doi:10.1016/j.chemosphere.2012.03.058

Cited by 35 publications

(23 citation statements)

References 43 publications

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“…The total release of TEQ to the environment may be even higher considering the increase of PCDD/Fs and TEQ concentrations during sunlight exposure of PCNB (Holt et al 2012). …”

Section: Resultsmentioning

confidence: 98%

“…For instance, the total production of PCNB in China was about 1,000 t a −1 (Wang 2010), and the usage of PCNB in the USA was estimated at 349-454 t a −1 (EPA 2006). The high volume use of such a pesticide may represent an important dioxin source to the environment in particular when considering that PCDD/Fs and TEQ levels increased when PCNB (and 2,4-D) are exposed to sunlight (Holt et al 2012). As indicated by the Australian Pesticides and Veterinary Medicines Authority (APVMA), a risk to health for workers applying the PCNB products in some situations will be caused by these impurities.…”

Section: Responsible Editor: Ester Heathmentioning

confidence: 98%

See 1 more Smart Citation

Unintentional formed PCDDs, PCDFs, and DL-PCBs as impurities in Chinese pentachloronitrobenzene products

Huang

Gao

et al. 2014

Environ Sci Pollut Res

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Pentachloronitrobenzene (PCNB) products have been reported to contain relatively high levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) as impurities. No data was available for Chinese PCNB products which are still produced and used in China. Therefore, we analysed Chinese PCNB products, including two raw pesticides and three formulations available on the market. In all samples, PCDDs, PCDFs, and dioxin-like polychlorinated biphenyls (DL-PCBs) were detected at levels exceeding Japanese regulation limits. The concentrations of PCDDs and PCDFs (0.16 to 0.93 ng TEQ g(-1)) were lower than the PCNB formulations measured from the Australian market (3.9 ng TEQ g(-1)). However, the Toxic Equivalent (TEQ) contribution from DL-PCBs (0.7 to 2.5 ng TEQ g(-1)) to total TEQ was higher compared to PCDDs and PCDFs. This discovery demonstrated that it is necessary to consider the DL-PCBs impurity in organochlorine pesticides and other organochlorine chemicals in particular chlorinated aromatic compounds for adequate risk assessment. In addition to DL-PCBs, other unintentionally POPs-hexachlorobenzene (HCB) (3.7 to 52 ng g(-1)) and pentachlorobenzene (PeCBz) (0.04 to 0.3 ng g(-1)) which are listed in the Stockholm Convention-were detected in the PCNB samples. The PCNB production steps were assessed for their unintentional POPs formation potential. Thermolysis of the aromatic compounds using iron chloride (FeCl3) as catalyst is suggested as relevant production step for (DL-)PCBs formation. Since the levels in the formulated PCNB recalculated to active ingredient were higher compared to the raw pesticide, the formulation process (e.g., milling) may also have had an influence on additional PCDD/Fs and PCBs formation.

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“…The total release of TEQ to the environment may be even higher considering the increase of PCDD/Fs and TEQ concentrations during sunlight exposure of PCNB (Holt et al 2012). …”

Section: Resultsmentioning

confidence: 98%

Section: Responsible Editor: Ester Heathmentioning

confidence: 98%

Unintentional formed PCDDs, PCDFs, and DL-PCBs as impurities in Chinese pentachloronitrobenzene products

Huang

Gao

et al. 2014

Environ Sci Pollut Res

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“…Whereas, with an exception for PCB-118, no dioxin-like compounds were addressed in the chemical analysis, substantial dioxin-like activities were observed in the Source, Gully, and Drain samples. These observations may be explained by polychlorinated dibenzo-p-dioxins and dibenzofurans impurities in pesticides (Holt et al 2010, Huang et al 2014, UNEP 2013 or formed from degradation of pesticides (Holt et al 2012) or other dioxin-like compounds present in pesticides (Huang et al 2014, Zahov et al 2014.…”

Section: Effect Profiling Of Pesticide Dumpsite Samplesmentioning

confidence: 92%

Effect-based assessment of persistent organic pollutant and pesticide dumpsite using mammalian CALUX reporter cell lines

Pieterse

Rijk²,

Simon

et al. 2015

Environ Sci Pollut Res

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A combined chemical and biological analysis of samples from a major obsolete pesticide and persistent organic pollutant (POP) dumpsite in Northern Tajikistan was carried out. The chemical analytical screening focused on a range of prioritized compounds and compounds known to be present locally. Since chemical analytics does not allow measurements of hazards in complex mixtures, we tested the use of a novel effect-based approach using a panel of quantitative high-throughput CALUX reporter assays measuring distinct biological effects relevant in hazard assessment. Assays were included for assessing effects related to estrogen, androgen, and progestin signaling, aryl hydrocarbon receptor-mediated signaling, AP1 signaling, genotoxicity, oxidative stress, chemical hypoxia, and ER stress. With this panel of assays, we first quantified the biological activities of the individual chemicals measured in chemical analytics. Next, we calculated the expected sum activity by these chemicals in the samples of the pesticide dump site and compared the results with the measured CALUX bioactivity of the total extracts of these samples. The results showed that particularly endocrine disruption-related effects were common among the samples. This was consistent with the toxicological profiles of the individual chemicals that dominated these samples. However, large discrepancies between chemical and biological analysis were found in a sample from a burn place present in this site, with biological activities that could not be explained by chemical analysis. This is likely to be caused by toxic combustion products or by spills of compounds that were not targeted in the chemical analysis.

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“…Therefore, using the annual dicofol production by this company, the annual amount of PCDD/Fs released to the environment could be the equivalent of up to 0.17 g I-TEQ. In addition, the concentrations of PCDD/Fs in dicofol were compared with other chlorine-containing organic compounds (Holt et al, 2012). The PCDD/F concentrations in dicofol are clearly lower than those in chloranil (Liu et al, 2012), but are equivalent to or a little higher than those in p-dichlorobenzene, 2,4-D and triclosan (Ni et al, 2005;Liu et al, 2013).…”

Section: Tablementioning

confidence: 99%

The release of persistent organic pollutants from a closed system dicofol production process

Yang

Ding

et al. 2014

Chemosphere

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h i g h l i g h t sPCDD/Fs and RDDTs in dicofol production process were analyzed. The inhalation of RDDTs in the workplace was evaluated. The emissions of RDDTs and PCDD/Fs in dicofol were calculated.The formation pathway of PCDD/Fs was discussed. a r t i c l e i n f o b s t r a c tHigh concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) have been found to be produced in chemical processes in which chlorine is a raw material. Samples of workshop air, waste water, waste acid, and the dicofol product were collected from a pesticide factory in China that uses a closed-system dicofol production process, and were analyzed for PCDD/Fs and RDDTs. The RDDTs concentrations were 1.88-17.53 lg m À3 in the workshop air samples, 4.85-456 lg kg À1 in the waste water and waste acid samples, and 4.74 g kg À1 in the dicofol product. The total estimated daily intakes of RDDTs for workers by inhalation in the workplace were in the range of 0.38-3.51 lg kg À1 bw d À1 for moderate activities. The annual amounts of RDDTs and p,p 0 -DDT directly released to the environment via the use of dicofol were 9480 kg and 1080 kg, respectively. The PCDD/F toxicity equivalent values (I-TEQs) in the waste water and waste acid samples ranged from 1.5 to 122 pg I-TEQ kg À1 and 86.3 ng I-TEQ kg À1 in the dicofol sample. The annual amount of PCDD/Fs released to the environment was 0.17 g I-TEQ. From the PCDD/F distribution patterns, it is suggested that the major pathway for PCDD/ F formation involves precursor synthesis during the production of dicofol in the closed-system process.

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Formation of dioxins during exposure of pesticide formulations to sunlight

Cited by 35 publications

References 43 publications

Unintentional formed PCDDs, PCDFs, and DL-PCBs as impurities in Chinese pentachloronitrobenzene products

Unintentional formed PCDDs, PCDFs, and DL-PCBs as impurities in Chinese pentachloronitrobenzene products

Effect-based assessment of persistent organic pollutant and pesticide dumpsite using mammalian CALUX reporter cell lines

The release of persistent organic pollutants from a closed system dicofol production process

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