Behaviour of alpha-, beta-, gamma-, and delta-hexachlorocyclohexane in the soil-plant system of a contaminated site

The behaviour of the organochlorine pesticide hexachlorocyclohexane (HCH) is investigated. The concentrations of alpha-, beta-, gamma-, and delta-HCH isomers were measured in soils, rhizosphere and vegetation in a contaminated area in Galicia (NW Spain). The total concentration of HCH in soils reached values close to 20,000 mgkg(-1). The plants analysed (Avena sativa L., Chenopodium spp., Solanum nigrum L., Cytisus striatus (Hill) Roth, and Vicia sativa L.) accumulated HCH, especially the beta-HCH isomer, in their tissues. The most likely mechanisms of HCH accumulation in plants were sorption of soil HCH on roots and sorption of volatilized HCH on aerial plant tissues. The concentrations of HCH obtained from the bulk and rhizosphere soils of selected plant species suggest that roots tend to reduce levels of the HCH isomers in the rhizosphere. The results reflect the importance of vegetation in the distribution of organochlorine compounds in the soil-plant system.     

Solid-state conformations and absolute configurations of (+) and (-) alpha-, beta-, and gamma-hexabromocyclododecanes (HBCDs)

Hexabromocyclododecanes (HBCDs) are high production volume chemicals used as flame retardants for plastics and textiles. They are currently produced in quantities exceeding 20,000 t/y. Despite this fact, the correct stereochemistry of most HBCDs is still not known. Six stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of different stereoisomers. Considering all elements of symmetry, 16 different stereoisomers including six pairs of enantiomers as well as 4 meso forms are possible theoretically. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and assigned their relative configurations. Herein, we report on the isolation of 6 enantiomerically pure alpha-, beta-, and gamma-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations, which were determined from X-ray diffraction analysis. The absolute configuration of (-) alpha-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the one of (+) beta-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) gamma-HBCD corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows the unambiguous identification of the six most important HBCD stereoisomers, which typically account for more than 95% of technical HBCDs. In addition, we compared the solid-state conformations of racemic and enantiomerically pure alpha-, beta-, and gamma-HBCDs. In all cases, vicinal dibromides adopted a synclinal (sc) conformation with torsion angles of 69+/-6 degrees. A unique structural motive was common to all examined HBCD solid-state conformations. This conserved structure was described as an extended triple turn consisting of an arrangement of three pairs of synclinal and two antiperiplanar torsion angles.     

The residual levels and health risks of hexachlorocyclohexanes (HCHs) and dichloro-diphenyl-trichloroethanes (DDTs) in the fish from Lake Baiyangdian, North China

The tissue and organs (muscle, brain, liver, and gill) of four species of freshwater fish from Lake Baiyangdian were analyzed for hexachlorocyclohexanes (HCHs) and dichloro-diphenyl-trichloroethanes (DDTs). The distribution characteristics were analyzed for HCHs and DDTs in various tissue and organs, which determined the health risks for humans. The research results showed that the wet weight content of all HCHs (∑HCHs) ranged from 0.05?～?14.53 ng?g^?1, with a mean of 3.47 ng?g^?1. The wet weight content of all DDTs (∑DDTs) ranged from ND to 8.51 ng?g^?1, with a mean of 2.41 ng?g^?1. For the various species of fish, the residual level of ∑HCHs was relatively higher in chub and grass carp and lowest in snakehead. The residual level of ∑DDTs was the highest in snakehead and did not exhibit a significant variance in the other three species. For the various tissues and organs, the contents of HCHs and DDTs were both highest in the fish liver, second highest in the fish gill, and lowest in the fish brain and muscle. Among the four types of isomers, the residual level of γ-HCH was relatively higher, while the residual level of α-HCH was the lowest. The content of p,p′-DDE was significantly greater to other forms of DDT and its isomer. The residual levels of HCHs and DDTs in fish were both below the national standard. However, the carcinogenic risk from the HCHs in parts of the tissue and organs of four fish species in Lake Baiyangdian exceeded the screen value threshold set by USEPA.     

Organochlorine pesticides (DDTs and HCHs) in soils from the outskirts of Beijing, China

Concentrations of HCH (hexachlorocyclohexane) and DDT (Dichlorodiphenyltrichloroethane) were determined in shallow subsurface (5-30 cm depth) and deep soil layers (150-180 cm depth) from the outskirts of Beijing, China. Concentrations of total HCHs (including alpha, beta, gamma, delta-isomers) and total DDTs (including p,p'-DDT, p,p'-DDE, p,p'-DDD, o,p'-DDT) in shallow subsurface soils ranged from 1.36 to 56.61 ng/g dw (median 5.25 ng/g), and from 0.77 to 2178 ng/g (median 38.66 ng/g), respectively, and those in the deeper layers were approximately an order of magnitude less. The spatial distribution of HCHs and DDTs reflected the known historical usage of these pesticides. No correlation between the concentrations of pesticides and soil organic matter content or clay content can be found. The factors affecting residue levels and compositions of DDT and HCH were discussed. The contour maps of beta/gamma ratios and DDT/DDE ratios for both the shallow subsurface and deep layer soils were drawn.     

Source,distribution, and health risk assessment of polycyclic aromatic hydrocarbons in urban street dust from Tianjin,China

To better assess and understand potential health risk of urban residents exposed to urban street dust, the total concentration, sources, and distribution of 16 polycyclic aromatic hydrocarbons (PAHs) in 87 urban street dust samples from Tianjin as a Chinese megacity that has undergone rapid urbanization were investigated. In the meantime, potential sources of PAHs were identified using the principal component analysis (PCA), and the risk of residents’ exposure to PAHs via urban street dust was calculated using the Incremental Lifetime Cancer Risk (ILCR) model. The results showed that the total PAHs (∑PAHs) in urban street dust from Tianjin ranged from 538 μg kg^?1 to 34.3 mg kg^?1, averaging 7.99 mg kg^?1. According to PCA, the two to three- and four to six-ring PAHs contributed 10.3 and 89.7 % of ∑PAHs, respectively. The ratio of the sum of major combustion specific compounds (ΣCOMB)?/?∑PAHs varied from 0.57 to 0.79, averaging 0.64. The ratio of Ant/(Ant?+?Phe) varied from 0.05 to 0.41, averaging 0.10; Fla/(Fla?+?Pyr) from 0.40 to 0.68, averaging 0.60; BaA/(BaA?+?Chry) from 0.29 to 0.51, averaging 0.38; and IcdP/(IcdP?+?BghiP) from 0.07 to 0.37, averaging 0.22. The biomass combustion, coal combustion, and traffic emission were the main sources of PAHs in urban street dust with the similar proportion. According to the ILCR model, the total cancer risk for children and adults was up to 2.55?×?10^?5 and 9.33?×?10^?5, respectively.     

HCHs and DDTs in salt marsh plants (Scirpus) from the Yangtze estuary and nearby coastal areas, China

HCHs and DDTs in salt marsh plants taken from intertidal flats in the Yangtze estuary and coastal area in April and July 2002 were determined by GC-ECD. A significant seasonal effect was observed for HCHs and DDTs in sources and concentration levels in different sample types including above-ground tissues and roots as well as the whole plants and rhizospheric sediments. The results indicated that the concentration of t-HCH was higher in the above-ground tissues than in their roots in April; however, the partitioning of DDTs between contaminated sediments and the roots showed the higher concentrations of t-DDT in their roots. HCHs and DDTs concentration levels were higher in above-ground tissues than in roots in July. BCFs of HCHs and DDTs exhibited lower values with higher levels of contaminants in sediments, and higher values with lower levels in sediments.     

Concentrations,properties, and health risk of PM2.5 in the Tianjin City subway system

A campaign was conducted to assess and compare the personal exposure in L3 of Tianjin subway, focusing on PM_2.5 levels, chemical compositions, morphology analysis, as well as the health risk of heavy metal in PM_2.5. The results indicated that the average concentration of the PM_2.5 was 151.43 μg/m³ inside the train of the subway during rush hours. PM_2.5 concentrations inside car under the ground are higher than those on the ground, and PM_2.5 concentrations on the platform are higher than those inside car. Regarding metal concentrations, the highest element in PM_2.5 samples was Fe; the level of which is 17.55 μg/m³. OC is a major component of PM_2.5 in Tianjin subway. Secondary organic carbon is the formation of gaseous organic pollutants in subway. SEM–EDX and TEM–EDX exhibit the presence of individual particle with a large metal content in the subway samples. For small Fe metal particles, iron oxide can be formed easily. With regard to their sources, Fe-containing particles are generated mainly from mechanical wear and friction processes at the rail–wheel–brake interfaces. The non-carcinogenic risk to metals Cr, Ni, Cu, Zn and Pb, and carcinogenic hazard of Cr and Ni were all below the acceptable level in L3 of Tianjin subway.

     

HCHs and DDTs in sediment-dwelling animals from the Yangtze Estuary, China

HCHs and DDTs in sediment-dwelling animals including mollusks and crabs from the Yangtze Estuary were determined by GC-ECD. Levels of t-HCH were in the range of 1.2-5.5 ng g(-1) and averaged 3.5 ng g(-1) in mollusks, while t-DDT concentrations ranged from 26.0 to 68.8 ng g(-1), with a mean of 34.5 ng g(-1). In crabs t-HCH concentrations varied from 2.0 to 25.7 ng g(-1) and averaged 13.8 ng g(-1), whereas the concentrations of t-DDT were in the range of 1.5-24.8 ng g(-1) with a mean value of 5.9 ng g(-1). The HCHs and DDTs levels depend on geographical position and sources, showing the high levels at fresh water area in the estuary, such as XP, CM and LHK sites, and lower at brackish water area, such as FX site, and little difference between species. Results also indicate there was no significant relationship between t-HCH (t-DDT) concentrations and lipid contents both in mollusks and crabs because of non-equilibrium state under a specific estuarine dynamics; smaller individuals accumulated more HCHs and DDTs than larger individuals of mollusks at LHK site, showing different uptake rate for these pesticides; moreover, HCHs and DDTs levels were lower in female crab bodies than male crab bodies suggesting that the release of spawning. BSAFs (Biota- Sediment Accumulation Factors) from sediment-dwelling animals for HCHs and DDTs show a significant "one high with two low" and "one low with two high" effect in the Yangtze Estuary.     

Distribution,sources, and ecological risk assessment of HCHs and DDTs in water from a typical coal mining subsidence area in Huainan,China

Environmental Science and Pollution Research - Coal mining subsidence areas are a special and widespread ecosystem in China and many developing countries in the world. However, limited research has...     

Chlorobenzenes and hexachlorocyclohexanes (HCHs) in the atmosphere of Bitterfeld and Leipzig (Germany)

Concentrations of tetrachlorobenzenes, pentachlorobenzene, hexachlorobenzene and alpha-, beta-, gamma- and delta-HCH in air and deposition were measured at three different contaminated sites in Greppin, Roitzsch (both near Bitterfeld) and Leipzig during five time intervals of 14 days in the summer months of 1998. The mean values of the chlorobenzene concentrations (gas phase and particle bound portions) over the whole sampling time were 0.11 ng/Nm3 (Leipzig), 0.17 ng/Nm3 (Roitzsch) and 0.37 ng/Nm3 (Greppin), the mean values of the HCH concentrations were 0.22 ng/Nm3 (Leipzig), 0.31 ng/Nm3 (Roitzsch) and 0.69 ng/Nm3 (Greppin). This increase of the concentration values from Leipzig over Roitzsch to Greppin indicates the influences of industrial waste sites in the Bitterfeld region on the atmospheric environment. The significantly higher values of hexachlorobenzene, alpha- and beta-HCH in Greppin are probably caused by emissions from the former chemical plant Bitterfeld-Wolfen and the landfill 'Antonie' near Greppin. Compared with literature data from other industrial impacted areas the measured air concentration and deposition values are relatively low.     

Lead (Pb) exposure and heart failure risk

Environmental Science and Pollution Research - Lead (Pb) is a heavy metal with widespread industrial use, but it is also a widespread environmental contaminant with serious toxicological...     

Organophosphate pesticide exposure and child health in China

Currently, organophosphate pesticides (OPs) are widely used for agriculture in China and around the world. A few epidemiological studies have examined the association between exposure to OPs and children’s health, but these studies reported inconsistent results. In view of the limitations of testing techniques and the intrinsic incompleteness of scientific evidence from current studies, we have considered some issues which may be interpreted and handled with caution.     

Human exposure to dioxins and furans: application of the substance flow analysis to health risk assessment

Substance Flow Analysis (SFA) is an important instrument that allows for the undertaking of environmental management for a specific contaminant. 'Control Analysis' is a tool that assesses the effect on a target flow of changes in flows forming part of a control basis set. The purpose of the present study was to perform a modeling of the annual PCDD/F flows in Tarragona Province and to apply the model for human health risk assessment. The validation of the model has been evaluated by comparing estimated fluxes with experimental values. Eleven subsystems, as well as a set of 88 flows of the system in Tarragona Province were considered. The total PCDD/F accumulation in Tarragona Province was between 62.6 and 159.5 g I-TEQ/y. Accumulation in sediments (27.9-74.6 g I-TEQ/y) and soils (35.0-80.8 g I-TEQ/y) are the two principal modes of deposition. Estimated flow in human adipose tissue means a mean intake of PCDD/F (via ingestion and inhalation) of 243 pg I-TEQ/person/day. The food chain pathway accounts for 99% of the total daily intake. As a result of the simulation, a 100% decrease in industrial emissions would cause a 1.7% reduction in the PCDD/F accumulation in humans. In turn, a 100% reduction of PCDD/Fs in the industrial waste waters would cause only an insignificant 0.1% decrease in the accumulation of PCDD/Fs in humans.     

Human health risk assessment of organochlorines associated with fish consumption in a coastal city in China

Food consumption is an important route of human exposure to organochlorines (OCs). In order to assess the potential health risks associated with these contaminants due to fish consumption, five species of fish were collected from a local market in Zhoushan City, an island in the East China Sea. Dioxin-like compounds, such as polychlorinated dibenzo-p-dioxins/ dibenzofurans, in the fish samples were screened by H4IIE-luc cell bioassay, and the concentrations of specific organochlorines were measured by gas chromatograph-electron capture detector (GC-ECD). The bioassay results indicated that concentrations of dioxin-like compounds in the fish samples were below detection limit (0.64 pg/mL). The concentrations of OC pesticides and PCBs ranged from 0.67 to 13 and 0.24 to 1.4 ng/g wet wt., respectively. Significantly, concentrations of p,p'-DDE in fish meat were comparatively high (average 3.9 ng/g wet wt.) compared with the other OC pesticides. The daily fish consumption, based on a dietary survey conducted among 160 local healthy residents, was determined to be 105 g/person. The relevant cancer benchmark concentrations of HCB, dieldrin, chlordane, DDTs and PCBs were 0.36, 0.04, 1.6, 1.7, and 0.29 ng/kg per day, respectively, based on the local diet. The hazard ratios (HRs), based on non-cancer endpoints were all less than 1.0, while the HRs based on cancer were greater than 1.0 for certain contaminants based on the 95th centile concentration in fish tissue.     

Health risk assessment of odors emitted from urban wastewater pump stations in Tianjin,China

In order to evaluate the potential adverse health effects of odor emissions from wastewater pump stations (WWPSs) to human, a health risk assessment was performed to study the odors emitted from an urban WWPS in a residential area, Tianjin (in North China). First, 15 types of volatile organic compounds in the WWPS were collected and analyzed using gas chromatography-mass spectrometry. Next, Monte Carlo probabilistic modeling was applied to evaluate the potential health effects of four odors (chlorobenzene, dichloromethane, hydrogen sulfide, and carbon disulfide), which had higher concentrations. The results revealed that the 95th percentile of the total non-carcinogenic risk was approximately 1.73, which poses a threat to human health. In addition, hydrogen sulfide had the highest non-carcinogenic risk value of the four; the hazard quotient of hydrogen sulfide was estimated to be 1.60 at the 95th percentile, higher than the upper confidence limit (1.0). The 95th percentile of the carcinogenic risk was approximately 5.47E-08, much lower than the maximum acceptable level (1.0E-06). Finally, the influence of the input variables on the output was evaluated using sensitivity analysis, and contaminant concentration, reference concentration, and inhalation unit risk were the most influential variables.     

Human health risk assessment of lead from mining activities at semi-arid locations in the context of total lead exposure

Lead from historical mining and mineral processing activities may pose potential human health risks if materials with high concentrations of bioavailable lead minerals are released to the environment. Since the Joint Expert Committee on Food Additives of Food and Agriculture Organization/World Health Organization withdrew the Provisional Tolerable Weekly Intake of lead in 2011, an alternative method was required for lead exposure assessment. This study evaluated the potential lead hazard to young children (0–7 years) from a historical mining location at a semi-arid area using the U.S. EPA Integrated Exposure Uptake Biokinetic (IEUBK) Model, with selected site-specific input data. This study assessed lead exposure via the inhalation pathway for children living in a location affected by lead mining activities and with specific reference to semi-arid conditions and made comparison with the ingestion pathway by using the physiologically based extraction test for gastro-intestinal simulation. Sensitivity analysis for major IEUBK input parameters was conducted. Three groups of input parameters were classified according to the results of predicted blood concentrations. The modelled lead absorption attributed to the inhalation route was lower than 2 % (mean?±?SE, 0.9 %?±?0.1 %) of all lead intake routes and was demonstrated as a less significant exposure pathway to children’s blood, compared with ingestion. Whilst dermal exposure was negligible, diet and ingestion of soil and dust were the dominant parameters in terms of children’s blood lead prediction. The exposure assessment identified the changing role of dietary intake when house lead loadings varied. Recommendations were also made to conduct comprehensive site-specific human health risk assessment in future studies of lead exposure under a semi-arid climate.     

Human exposure to dioxins through the diet in Catalonia,Spain: carcinogenic and non-carcinogenic risk

The main objectives of this study were to estimate the dietary intake of dioxins by the population of Catalonia, Spain, to determine which food groups showed the greatest contribution to this intake, and to assess the health risks potentially associated with the dietary dioxin intake. From June to August 2000, food samples were randomly acquired in seven cities of Catalonia. Dioxin concentrations were determined in 108 samples belonging to the following groups: vegetables, fruits, pulses, cereals, fish and shellfish, meats and meat products, eggs, milk and dairy products, and oils and fats. Estimates of average daily food consumption were obtained from recent studies. Total dietary intake of dioxins for the general population of Catalonia was estimated to be 95.4 pg WHO-TEQ/day (78.4 pg I-TEQ/day), with fish and shellfish (31%), diary products (25%), cereals (14%) and meat (13%) showing the greatest percentages of contribution to dioxin intake. The contribution of all the rest of food groups to the total dietary intake was under 20%. The non-carcinogenic risk index of dioxin intake through the diet was in the range 0.34-1.36, while the carcinogenic risk level was 1,360 excess cancer over a lifetime of 70 years. Our results corroborate the decreasing tendency in dietary intake of dioxins found in recent studies (2000-2001) from various countries.     

Characterization of HCHs and DDTs in urban dustfall and prediction of soil burden in a metropolis-Beijing, China

The concentrations, spatial distribution and compositional patterns of extensively used hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) in urban dustfall in a metropolis-Beijing are presented in this paper. The potential sources are discussed and soil burdens are predicted based on the fluxes. The hotspots in commercial areas are identified by spatial distribution maps and the fractional value isomers indicates that dustfall in urban Beijing are affected by both current and historical usage of DDTs. It is worth noticing that there is possible application "dicofol-type of DDTs" in Beijing. The measured atmospheric deposition flux is 1.14×10(5) ng h(-1) m(-2) for HCHs and 1.47×10(5) ng h(-1) m(-2) for DDTs, respectively. However, when compared with atmospheric deposition flux, the volatilization flux estimated from concentrations in soils by fugacity model is significantly lower for HCHs (2.41 ng h(-1) m(-2)) and DDTs (0.07 ng h(-1) m(-2)). The net atmospheric flux to the soil suggests that the levels of HCHs and DDTs in soil are dominated by atmospheric deposition and the urban soil in Beijing would be a sink for HCHs and DDTs in the long term.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.     

The levels of polycyclic aromatic hydrocarbons (PAHs) in human milk and exposure risk to breastfed infants in petrochemical industrialized Lanzhou Valley,Northwest China

Environmental Science and Pollution Research - We investigated in this paper the presence of PAHs in human milk from lactating women residing in Lanzhou, a petrochemical industrialized valley city...