Profiles and determinants of dicofol, endosulfans, mirex, and toxaphenes in breast milk samples from 10 prefectures in Japan.

Human exposure to persistent organic pollutants (POPs) is reflected by POP concentrations in breast milk. Many studies of POPs in breast milk have been performed in Japan, but insufficient information is available about some legacy POPs (e.g., mirex and toxaphenes, included in the Stockholm Convention in 2001) and novel POPs (e.g., dicofol and endosulfans, included in the Stockholm Convention in 2019 and 2011, respectively). In this study, dicofol, endosulfan, mirex, and toxaphene concentrations in breast milk from 10 prefectures in Japan were determined. The samples were collected between 2005 and 2010, before Stockholm Convention restrictions on endosulfans and mirex were implemented. Common POPs (e.g., polychlorinated biphenyls) were also analyzed to allow the contamination statuses to be compared. The α-endosulfan and ß-endosulfan concentrations were 0.26-13 and 0.012-0.82 ng/g lipid, respectively. The toxaphene #26 and #50 concentrations were <0.08-5.6 and < 0.1-8.5 ng/g lipid, respectively. The dicofol concentrations were <0.01-4.8 ng/g lipid. The mirex concentrations were <0.2-3.5 ng/g lipid. The α- and ß-endosulfan concentrations on a lipid weight basis negatively correlated with the lipid contents of the milk samples (ρ = -0.65, p < 0.01 for α-endosulfan; ρ = -0.58, p < 0.01 for ß-endosulfan). The toxaphene concentrations positively correlated with the lipid contents. The mirex concentrations positively correlated with the maternal age but negatively correlated with the maternal body mass index. No correlations between the dicofol concentrations and the factors were found. Principal component analysis divided the data into four groups, (1) chlordanes, dichlorodiphenyltrichloroethanes and related compounds, hexachlorobenzene, hexachlorocyclohexanes, hexachloroethane, and polychlorinated biphenyls, (2) endosulfans, (3) dicofol, dieldrin, and toxaphenes, and (4) bromodiphenyl ether 47. This indicated that bromodiphenyl ether 47, dicofol, endosulfans, and toxaphenes have different exposure routes or different kinetics to the other legacy POPs.

Levels and distribution of dechloranes in sediments of Lake Taihu, China.

The occurrence and spatial distribution of dechloranes including mirex, dechlorane plus (DP), dechlorane (Dec) 602, Dec 603, and Dec 604 in surficial sediments of Lake Taihu were investigated in this study. The concentrations of mirex and DP ranged from below detection limit (BDL) to 1.29 ng g(-1) dw and 0.051 to 2.10 ng g(-1) dw, respectively. Dec 602, Dec 603, and Dec 604 on the other hand, were BDL in any of the samples. The contamination levels of DP were higher than that of Mirex at 21 of all 22 sampling sites. Levels of mirex and DP in the lake sediments were correlated when an extremely high mirex value was removed. Both mirex and DP levels were correlated with the amount of organic matters in the sediment samples. Spatial distribution of mirex and DP suggested that these two chemicals in the lake had similar input sources except for one site. Comparison to previously reported flame retardants' levels in the sediments shows that DP levels were similar with the levels of tetrabromobisphenol A, hexabromocyclododecane but lower than PBDEs and organophosphates levels in Lake Taihu. The higher levels in the north-east part of Lake Taihu adjacent to two major cities: Wuxi and Suzhou, indicated that city effluent might be a major source for DP contamination in the lake.

Identification and occurrence of analogues of dechlorane 604 in Lake Ontario sediment and their accumulation in fish.

The dechlorane family of flame retardants, which includes Mirex (also known as Dechlorane), Dechlorane Plus (DP), and Dechloranes (Dec) 602, 603, and 604, were manufactured at a facility along the Niagara River, upstream of Lake Ontario. Some of these compounds remain in use. In a previous study, we found Mirex and Dec602 to have greater bioaccumulation potentials than Dec604 and DP based on calculated biota-sediment accumulation factors (BSAFs). In this study, analogues of Dec604, containing fewer bromines and mixed substitutions of bromine and chlorine, were identified in Lake Ontario sediment and fish using high and ultrahigh resolution mass spectrometric techniques. The tribromo-Dec604 (Br3Dec604) analogue, known as Dechlorane 604 Component B (Dec604 CB), was present in lake trout and whitefish at concentrations of 10-60 ng/g lipid weight, approximately 50-200 times greater than concentrations measured for Dec604. In addition, BrDec604 and Br2Dec604 analogues, and mixed Br2Cl2Dec604, Br3ClDec604, Br2ClDec604, and BrCl2Dec604 analogues were also present. We have shown that solutions of Dec604 and Dec604 CB exposed to UV-light undergo photodebromination and give rise to the analogues found in sediment and fish. Dec604 CB and other lesser halogenated analogues of Dec604 show greater bioaccumulation potentials than Dec604, Dec602 and DP, based on BSAFs, which highlight the need to consider likely impurities and degradation products in the assessment of persistent, bioaccumulative, and toxic compounds.

Assessment of Dechlorane compounds in foodstuffs obtained from retail markets and estimates of dietary intake in Korean population.

A total of 175 samples, composed of 35 different foodstuffs, were obtained from retail markets in Korea and analyzed to investigate the contamination status and dietary intake of Dechlorane compounds. The concentrations of Dechlorane Plus (DP), mirex, Dechlorane (Dec) 602 and 603 ranged from ND to 169.85 pg/g wet weight (ww), 107.30 pg/g ww, 20.81 pg/g ww, 0.41 pg/g ww, respectively, while Dechlorane (Dec) 604 was not detected in any samples. Strong correlations between anti- and syn-DP and between mirex and Dec 602 were observed. The average anti-isomer fractional abundance (fanti) was 0.78±0.11 which was larger than the technical DP value (fanti=0.75). The estimated dietary daily intake of DP, 11.2×10(3) pg/day, was one to three orders of magnitude higher than other Dechloranes. Grain was the most contributed food group to dietary daily intake of DP for Korean population.

Mechanochemical destruction of mirex co-ground with iron and quartz in a planetary ball mill.

Mechanochemical destruction (MCD) has been recognized as a promising non-combustion technology for the disposal of obsolete pesticides belonging to the persistent organic pollutants (POPs). Mirex, a termiticide ever used for many years in China, was ball milled in the presence of various reagent(s) in a planetary ball mill at room temperature to investigate the destruction efficiency. The ground samples were characterized and analyzed by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, gas chromatography (GC), and ion chromatography (Martins, Bicego et al.). Under the same conditions of mill rotary rate and charge ratio, the mixture of iron powder and quartz sand (Fe/SiO(2)) was found best in promoting the mirex destruction. Mirex was completed destroyed after 2 h grinding at a charge ratio of 36:1 (reagent/mirex, m/m) and a mill rotation speed of 550 rpm. No organic compound was detected by GC/µECD screening. The yield of water-soluble chlorine determined by ion chromatography (Martins, Bicego et al.) in the final residue accounted for 90.7% of chlorine in the original mirex, which indicated a nearly complete dechlorination. Signals of both graphite and amorphous carbon were found in the Raman spectra of the co-ground powder samples. With the main final degradation products of water soluble Cl and carbon, the mechanism of the mechanochemical destruction approach should be dechlorination followed by the carbonization.

East versus West: organic contaminant differences in brown pelican (Pelecanus occidentalis) eggs from South Carolina, USA and the Gulf of California, Mexico.

Brown pelicans (Pelecanus occidentalis) were listed as endangered in the United States in 1970, largely due to reproductive failure and mortality caused by organochlorine contaminants, such as DDT. The southeast population, P.o. carolinensis, was delisted in 1985, while the west coast population, P.o. californicus, was not delisted until 2009. As fish-eating coastal seabirds, brown pelicans may serve as a biomonitors. Organic contaminants were examined in brown pelican eggs collected from the Gulf of California in 2004 and South Carolina in 2005 using gas chromatography/mass spectrometry (GC/MS). Contaminants were compared using all individual data as well as statistically pooled samples to provide similar sample sizes with little difference in results. Principal components analysis separated the Gulf of California brown pelican eggs from the South Carolina eggs based on contaminant patterns. The South Carolina population had significantly (P<0.05) higher levels of polychlorinated biphenyls (PCBs), chlordanes, dieldrin and mirex, while the Gulf of California eggs had higher levels of dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs). With the exception of dieldrin and brominated diphenyl ether (BDE) 47, this pattern was observed for mussel and oyster tissues from these regions, indicating the need for further study into the differences between east and west coast brown pelican populations and ecosystem contamination patterns.

Differences between Arctic and Atlantic fjord systems on bioaccumulation of persistent organic pollutants in zooplankton from Svalbard.

Differences in bioaccumulation of persistent organic pollutants (POPs) between fjords characterized by different water masses were investigated by comparing POP concentrations, patterns and bioaccumulation factors (BAFs) in seven species of zooplankton from Liefdefjorden (Arctic water mass) and Kongsfjorden (Atlantic water mass), Svalbard, Norway. No difference in concentrations and patterns of POPs was observed in seawater and POM; however higher concentrations and BAFs for certain POPs were found in species of zooplankton from Kongsfjorden. The same species were sampled in both fjords and the differences in concentrations of POPs and BAFs were most likely due to fjord specific characteristics, such as ice cover and timing of snow/glacier melt. These confounding factors make it difficult to conclude on water mass (Arctic vs. Atlantic) specific differences and further to extrapolate these results to possible climate change effects on accumulation of POPs in zooplankton. The present study suggests that zooplankton do biomagnify POPs, which is important for understanding contaminant uptake and flux in zooplankton, though consciousness regarding the method of evaluation is important.

Concentration and bioaccumulation of dechlorane compounds in coastal environment of northern China.

Dechloranes, including Dechlorane Plus (DP), Mirex (Dechlorane), Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), and Dechlorane 604 (Dec 604), were determined using GC-MSD for water, sediment and oyster samples collected at 15 sampling sites near the Bohai and Huanghai Sea shore area of northern China in 2008. DP and Mirex were detected in most water, sediment, and oyster samples, which indicated widespread distribution of these two compounds. The mean concentrations in water, sediment and oyster samples, respectively, were 1.8 ng/L, 2.9 ng/g dry weight (dw) and 4.1 ng/g wet weight (ww) for total DP, and 0.29 ng/L, 0.90 ng/g dw, and 2.0 ng/g ww for Mirex. Dec 602 and Dec 603 were not detected in water but in small portions of the sediment and oyster samples, showing a low level of contamination by these two chemicals in the region. Strong and significant correlations were found between total DP and Mirex concentrations in water, sediment and oyster samples, probably suggesting similar local sources of these two chemicals. Dec 604 was not found in any samples. The biota-sediment accumulation factor (BSAF) of DP, Mirex, and Dec 602 declined along with the increase of their logarithm of octanol-water partition coefficients (log Kow), possibly indicating that compounds with lower log Kow (like Mirex and Dec 602) accumulated more readily in biota. The mean fractional abundance of syn-DP (fsyn) was 0.34 in water samples, a value lower than that in Chinese commercial mixture (0.41), while the mean fsyn for surface sediment (0.44) and oyster (0.45) samples were higher than technical values. Enrichment of syn-DP in oyster was in agreement with previously reported findings in Great Lakes fish. Enrichment of syn-DP in marine surface sediments, however, is contrary to data reported for fresh water sediments. To our knowledge this is the first report of Dec 602, Dec 603, and Dec 604 in a marine environment and also the first report of Dechloranes in marine biota.

HRGC/HRMS analysis of mirex in soil of Liyang and preliminary assessment of mirex pollution in China.

China is a country with the most severe termite damage in the world. Mirex is one of the two effective orgochlorine pesticides used in China for termite control. A high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was employed for mirex analysis in soil samples from Liyang city, which once was an important mirex production base in China. The detected mirex levels in soil in Liyang were 2.9-4300pgg(-1)dw (dry weight), with the geometric mean 26.83pgg(-1)dw and the geometric standard deviation 5.02. The highest level occurred at the site near the Liyang Guanghua Chemical Factory. It implies the contribution of industrial activities to the mirex pollution in the surrounding environment. However, the factory only influenced very limited adjacent areas. A Level III fugacity model was developed to study the mirex pollution in Chinese provinces. The results show that the highest concentration occurred in Jiangxi Province, which has the largest consumption of mirex among Chinese provinces. On a regional scale, the calculated concentrations of mirex in the environment are generally so low that it indicates no harm to human and organisms. The total amount of mirex in the environment in China was estimated to be about 25.12tons, most of which exists in soil.

Temporal trends of legacy POPs in Arctic biota, an update.

A statistically robust method was applied to 316 time-series of 'legacy' persistent organic pollutants (POPs) in Arctic biota from marine, freshwater and terrestrial ecosystems with the purpose of generating a 'meta-analysis' of temporal trend data collected over the past two to three decades for locations from Alaska in the west to northern Scandinavian in the east. Information from recently published temporal trend studies was tabulated and comparisons were also drawn with trends in arctic air. Most of the analysed time-series of legacy POP compounds showed decreasing trends, with only a few time-series showing significantly increasing trends. Compounds such as alpha-HCH, gamma-HCH and SigmaDDT had a relatively high proportion of time-series showing significantly decreasing trends; SigmaCHL had the lowest proportion. beta-HCH was an exception, where long-range transport through the ocean, and not the atmosphere, may explain several increasing trends that were detected in the Canadian Arctic. Moving east from the Canadian Arctic there was a trend towards a greater proportion of significantly decreasing trends. Several time-series for DDE and SigmaDDT showed significantly non-exponential trends, most often with a period of relative stability followed by a decrease. The median 'minimum detectable annual change within a 10-year period' for all of the time-series considered was 12% which did not meet the desirable level of statistical power capable of detecting a 5% annual change with a significance level of 5% within a 10-year period. The trends observed in the biota were consistent with decreasing trends of legacy POPs reported for Arctic air which appear to follow historic decreases in emissions. However, recent decreases in air are also starting to show signs of levelling off which may be an indication that atmospheric concentrations and, consequently those in the biota, are being less driven by primary sources and more by environmental processes and degradation.

First investigations of mountainous cold condensation effects with the CliMoChem model.

We present first results of a modeling study to explore the occurrence and extent of cold condensation effects in mountains with the CliMoChem model for a group of substances with different volatility and persistence. The mountainous region is set up in a generic way by modifying the precipitation rate and annual temperature course in a northern temperate zone. The results illustrate substance-specific tendencies to exhibit a cold condensation. While strong effects are observed for alpha-hexachlorocyclohexane and PCB-28, the less volatile compounds mirex and PCB-180 are less susceptible to mountainous cold condensation. An analysis of the temporal trends in concentrations indicates that mountain ranges first act as cold condensers, but may eventually become secondary emitters. Limitations of the modeling approach used are discussed and an outlook on further steps of model development and application is given.

Spatial and temporal trends in surface water and sediment contamination in the Laurentian Great Lakes.

Data from recent sediment and surface water surveys have been collated and mapped to illustrate the spatial distribution of contaminants across the entire Great Lakes basin. Information from historical surveys, together with data from surface water monitoring programs in three major connecting channels, has also been collated in order to evaluate temporal trends. In general, Lakes Superior and Michigan exhibited the lowest levels of sediment contamination while Lake Ontario had the highest. Contaminants such as gamma-HCH (lindane) and dieldrin were ubiquitous in surface waters across the entire basin, which was indicative of atmospheric sources. The distribution of other compounds including hexachlorobenzene, octachlorostyrene and mirex indicated the presence of local sources within the watersheds of the connecting channels. Surficial sediment contamination was found to have decreased markedly since the late 1960s and 1970s. Similarly, surface water contamination decreased over the period 1986-1997 with concentrations of dieldrin, hexachlorobenzene, octachlorostyrene and mirex reduced by over 50%. However, the spatial distributions of both sediment and surface water contamination indicate that further effort is warranted in reducing local sources of contaminants, particularly in Lake Ontario.

The association between local fish consumption and DDE, mirex, and HCB concentrations in the breast milk of Mohawk women at Akwesasne.

A study was conducted to assess the extent to which the consumption of local fish contaminated with p,p'-dichlorodiphenyl dichloroethylene (p,p'-DDE), mirex, and hexachlorobenzene (HCB) has impacted the concentrations of these compounds in the milk of nursing Mohawk women residing along the St. Lawrence River. From 1986 to 1992, 97 Mohawk women were interviewed, and each donated a one-time sample of at least 50 ml of breast milk. The comparison population consisted of 154 Caucasians from other rural areas in New York State. After adjustment for potential confounders, Mohawk mothers who gave birth from 1986 to 1990 had significantly higher geometric mean p,p'-DDE milk concentrations than did the control group, but no significant differences were observed from 1991 to 1992. In contrast, mirex was significantly elevated among the Mohawks throughout the study period, while HCB showed no difference at any point. Mohawk women with the greatest estimated cumulative lifetime exposure to p,p'-DDE from local fish consumption had a significantly higher geometric mean milk level of that compound relative to control women, but no differences in mirex or HCB concentrations in breast milk by local fish consumption were found. The reduction in breast milk p,p'-DDE concentrations among the Mohawk women from 1986 to 1990 parallels a corresponding decrease in local fish consumption, and may be the result of the advisories that have been issued over the past decade recommending against the consumption of local fish by pregnant and nursing Mohawk women. Elevations in the concentrations of mirex in the breast milk of the Mohawks are consistent with the fact that it is a common contaminant in the region and throughout the Lake Ontario-St. Lawrence River Basin.

Comparison of PCB congeners and pesticide levels between serum and milk from lactating women.

Samples of blood and milk were obtained from lactating women participating in the New York State Angler study. A total of seven women gave one blood and one milk sample at time intervals between blood and milk collection different for each woman. The time between samples varied from 3 to 318 days. One subject provided a second milk sample 219 days after the first milk sample. The samples were analyzed for 69 PCB congeners, DDE (a metabolite of DDT), Mirex, and hexachlorobenzene (HCB). Lipid content was determined by gravimetric analysis. The congener profiles in serum and milk were similar for each individual but different among all subjects. The sum of the concentrations of the congeners present above the limit of detection was used to estimate the total PCB concentration that was in the range of 2.6 to 5.8 ng/g of serum and 3.5 to 14.1 ng/g of milk. The ratio of serum to milk concentrations varied from 0.18 to 1.66 with a mean of 0.65+/-0.49 showing no consistency among individuals prior to adjusting the data for lipid content. The total PCB levels normalized for lipid content were 320-728 ng/g of serum lipid and 239-428 ng/g of milk lipid. The range of the lipid adjusted serum/milk ratio was 1.1 to 2.8 and the mean+/-SD serum/milk ratio was 1.9+/-0.5. The ranges of lipid adjusted serum concentration of DDE, HCB, and Mirex were 95 to 591, 8 to 48, and 3 to 29 ng/g lipid, respectively. The ranges of lipid adjusted milk concentration of DDE, HCB, and Mirex were 90 to 577, 11 to 22, and 1 to 10 ng/g lipid, respectively. For DDE, HCB, and Mirex, the means of the individual lipid adjusted serum to milk ratios were 1.5+/-0.7, 2.5+/-1.5, and 5. 3+/-4.6, respectively. Considerable differences were found among lipid adjusted concentrations of these environmental pollutants in serum and milk samples from the same individual. This suggests that body burden estimates in lactating women using different matrices may not be equivalent even when lipid adjusted values are used.

The human body burden of mirex in the southeastern United States.

Mirex is an organochlorine chemical with pesticidal and other industrial usages. Biologically, mirex was used as an insecticide for the control of imported fire ants in large areas of the southeastern United States. Evidence of mirex exposure in a national survey of chemicals in adipose tissue led to a more intensive survey of the general population in treated counties of the southeastern United States. Forty sites were selected randomly from 8 southeastern states where mirex was used widescale to combat fire ants; a total of 624 adipose tissue specimens were collected from these 40 sites. Tissue specimens were prepared by a modified Mills-Onley-Gather procedure and analyzed for mirex and selected other organochlorine compounds by electron-capture gas chromatography. Positive residue findings were confirmed by combined gas chromatography and mass spectrometry. Weighted statistical analysis of the data was conducted to estimate the level of mirex in the study area. It was estimated that 10.2% of the population of southern United States had quantifiable levels of mirex in adipose tissue. The estimated geometric mean of the quantifiable residue amounts was 0.286 ppm (lipid basis). Statistical tests of association and regression were used to investigate possible relationships between the presence and levels of mirex, and the Census Division or state of tissue-specimen collection, by age, race, and sex. These analyses indicated that region or location of tissue specimen collection (assumed to be area of residence) strongly related to both the presence of mirex residue and the amount of mirex residue detected. This may be correlated with the amount of mirex applied for fire ant control or with some other exposure patterns in different regions.