Comparison of micrometeorological and two-film estimates of air–water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago

The air-sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.     

Residues of organochlorine pesticides in Alabama soils

A survey was made of 36 Alabama agricultural soils to assess residues of formerly used organochlorine pesticides. Compounds determined comprised alpha- and gamma-hexachlorocyclohexane, heptachlor, heptachlor-exo-epoxide, trans- and cis-chlordane, trans-nonachlor, dieldrin, toxaphene, DDT and DDE. Concentrations varied by several orders of magnitude among farms and appeared to be log-normally distributed. Highest concentrations (ng g(-1) dry soil, arithmetic means) were found for toxaphene (285+/-390) and DDTs (p,p'-DDE, 22.7+/-21.4; p,p'-DDT, 24.6+/-30.5; o,p'-DDT, 4.00+/-5.86; p,p'-DDD, 2.40+/-2.41) which were once heavily used in the southern USA. Pesticide residues were not proportional to soil organic carbon content indicating that residue concentrations were a reflection of pesticide application history and dissipation rates rather than air-soil equilibrium. Mean ratios of DDT/DDE in six regions of the state ranged from 0.39 to 1.5, and compound ratios for chlordanes and toxaphene were different from those in the technical mixtures.     

Determination of vapor pressures for chloroguaiacols,chloroveratroles, and nonylphenol by gas chromatography

Vapor pressures of six chlorinated phenols were measured by capillary gas chromatography using a 1.0-m BP-1 bonded phase column. GC-determined vapor pressures (P_GC) were correlated with known liquid-phase vapor pressures (P_L) by the equation: Log P_GC = 1.026 Log P_L — 0.132, r² = 0.975 (vapor pressures in pascals). This relationship was used to estimate P_L for chloroguaiacols, chloroveratroles, and 4-nonylphenol from their experimental P_GC.     

Soil-air exchange of organochlorine pesticides in the Southern United States

Soil samples were collected from 30 farms in Alabama, Louisiana and Texas during 1999-2000 to determine residues of organochlorine pesticides (OCPs). One or more of the DDT compounds (p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, o,p'-DDE) was above the quantitation limit (0.1 ng g(-1) dry weight) in every soil, and toxaphene was above the quantitation limit (3 ng g(-1)) in 26 soils. Chlordanes, dieldrin and hexachlorocyclohexane (HCH) isomers occurred less frequently (quantitation limits 0.1 ng g(-1) for dieldrin and 0.05 ng g(-1) for chlordanes and HCHs). OCPs were measured in air at 40 cm above the soil at selected farms to investigate soil-air partitioning. Concentrations of OCPs in air were positively and significantly (P<0.001-0.004) correlated to soil concentrations for toxaphene, p,p'-DDT, o,p'-DDT, p,p'-DDE, dieldrin, and trans-nonachlor. The regression was weaker (P=0.022) for cis-chlordane and not significant for trans-chlordane (P=0.43) nor gamma-HCH (P=0.80). Approach to soil-air equilibrium was assessed by calculating fugacities in the soil and air (f(s) and f(a)) for samples with quantifiable residues in both compartments. The fugacity fraction f(s)=0.5 at equilibrium and is <0.5 or >0.5 for net deposition and net volatilisation, respectively. Fugacity fractions varied greatly for different soil-air pairs, reflecting generally disequilibrium conditions. Mean fugacity fractions indicated near-equilibrium for some OCPs (p,p'-DDE, chlordanes, trans-nonachlor and dieldrin) and net volatilisation for others (p,p'-DDT, o,p'-DDT, toxaphene, gamma-HCH). Chiral analysis showed that enantioselective degradation of (+) or (-) o,p'-DDT in soil was accompanied by enrichment or depletion of the corresponding enantiomers in the overlying air, although there appeared to be some dilution by racemic o,p'-DDT from regional air transport.     

Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment

Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011–2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069–2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air–sea gas exchange and “bulk” (precipitation + dry particle) deposition, resulting in net gains of 53 and 46 kg year^?1 for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year^?1 for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.     

Henry's law constants for hexachlorobenzene, p,p'-DDE and components of technical chlordane and estimates of gas exchange for Lake Ontario

The Henry's law constants (HLC) for trans- and cis-chlordane (TC, CC), trans-nonachlor (TN), hexachlorobenzene (HCB) and p,p'-DDE were determined by the gas-stripping method over a temperature range of 5-35 degrees C. The HLC variation versus temperature (K) was described by logH=m/T+b. Parameters of this equation were (with standard deviations) TC: m=-1524+/-158, b=6.58+/-0.54; CC: m=-1786+/-209, b=7.42+/-0.71; TN m=-2068+/-284, b=8.44+/-0.97; HCB: m=-3013+/-174, b=11.60+/-0.59 and p,p'-DDE: m=-2043+/-240, b=8.37+/-0.82. The HLCs (Pa m3 mol(-1)) at 25 degrees C (298.15 K) were: TC=29; CC=27; TN=32; p,p'-DDE=33 and HCB=35. These HLCs values were used to calculate fugacity ratios from paired air and water data from Lake Ontario, July 1998. The resulting fugacity ratios predict that volatilization was occurring for all compounds during that month.     

Hydroxypropyl-β-cyclodextrin as non-exhaustive extractant for organochlorine pesticides and polychlorinated biphenyls in muck soil

Hydroxypropyl-β-cyclodextrin (HPCD) was used as a non-exhaustive extractant for organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in muck soil. An optimized extraction method was developed which involved using a HPCD to soil mass ratio of 5.8 with a single extraction period of 20 h. An aging experiment was performed by spiking a muck soil with ¹³C-labeled OCs and non-labeled PCBs. The soil was extracted with the optimized HPCD method and Soxhlet apparatus with dichloromethane over 550 d periodically. The HPCD extractability of the spiked OCs was greater than of the native OCs. A decreased in HPCD extractability was observed for the spiked OCs after 550 d of aging and their extractability approached those of the natives. The partition coefficient between HPCD and soil (log K_CD-Soil) was negatively correlated with the octanol-water partition coefficient (log K_OW) with r² = 0.67 and p < 0.05.     

Occurrence and vapor particle partitioning of heavy organic compounds in ambient air in Brazzaville, Congo

High volume air samples for organochlorine (OC) pesticides, polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) were collected during August-September 1989 in Brazzaville, Congo (4.14 degrees S, 15.14 degrees E). Average concentrations (ng/m3) were SigmaDDT=2.8; Sigma HCH (hexachlorocyclohexane)=0.42; Sigmachlordane=0.027; SigmaPCB=0.55 Sigma3-6 ring PAH=42; total DDT concentrations in Brazzaville fell between those reported in Porto Novo and Delhi (India) and were 20-100 times higher than those found in US cities. The average gamma-HCH to alpha-HCH ratio (11) indicated use of lindane instead of technical HCH. The similarities between chlordane levels in Brazzaville and the open ocean indicated that little or no local use occurs. PAH levels were about equal to or lower than those reported in US cities, whereas PCB levels were three times lower. Vapor/particle distribution coefficients for several OC and PAH were in good correlation with their vapor pressures. The fraction of PAH on particles was greater than that of OC pesticides.     

Organochlorine contaminants in narwhal (Monodon monoceros) from the Canadian Arctic

Organochlorine pesticides (DDT, chlordane, polychlorinated camphenes (PCCs), dieldrin, hexachloroheclohexanes (SigmaHCH), mirex), polychlorinated biphenyl congeners (PCBs) and chlorobenzenes (SigmaCBz) were determined in blubber and liver of narwhal (Monodon monoceros) collected during 1982-1983 from Pond Inlet on northern Baffin Island in the Canadian Arctic. PCCs were the predominate organochlorines in narwhal blubber, ranging in concentration from 2990 to 13 200 ng g(-1) (wet wt) in males and from 1910 to 8390 ng g(-1) in females. PCCs consisted of two major components, an octachlorobornane and a nonachlorobornane with gas chromatographic retention times of 1.05 and 1.22, relative to 4,4'-DDE. SigmaPCB concentrations in blubber ranged from 2250 to 7290 ng g(-1) in males and from 894 to 5710 ng g(-1) in females. Seven PCB congeners (tetra-, penta- and hexachlorobiphenyls) accounted for 45% of total PCB (SigmaPCB) in narwhal blubber. Narwhal had 1.4- to 8.6-fold higher ratios of tetra- and pentachlorobiphenyls to PCB-153 (2,2',4,4',5,5'-hexachlorobiphenyl), lower 4,4'-DDE/SigmaDDT ratios and lower proportions of trans-nonachlor to total chlordane components than reported for odontocetes living in more contaminated environments. Mean SigmaPCB concentrations in narwhal were 6- to 15-fold lower than in dolphins from the Canadian east coast and belugas from the St Lawrence River estuary, respectively, while PCC levels were from 4- to about 2-fold lower, and SigmaHCH, dieldrin and SigmaCBz differed by <2-fold. The pattern of organochlorines in narwhal tissues suggests they are exposed to proportionally more volatile compounds, and may have less capacity to metabolize some of these compounds, relative to odontocetes living nearer sources of these contaminants.     

Chiral analysis of organochlorine pesticides in Alabama soils.

The enantiomeric composition of organochlorine (OC) pesticide residues was investigated in 32 agricultural and 3 cemetery soils from Alabama. The enantiomeric signatures were similar to those from other soils in US and Canada. The enantiomer fractions (EFs) of o,p'-DDT showed great variability, ranging from 0.41 to 0.57 while the EFs of chlordanes and chlordane metabolites were less variable and differed in general significantly from racemic. Enantioselective depletion of (+)trans-chlordane, (-)cis-chlordane, the first eluting enantiomer of MC5, and enrichment of (+)heptachlor-exo-epoxide and (+)oxychlordane was found in a large majority of the samples with detectable residues. The enantiomeric composition of alpha-hexachlorocyclohexane was racemic or close to racemic.