Chubashini Shunthirasingham

Spatial and temporal pattern of pesticides in the global atmosphere

As part of the Global Atmospheric Passive Sampling (GAPS) study, XAD-resin based passive samplers are being deployed for consecutive one-year periods at numerous sites on all seven continents to determine annually averaged concentrations of persistent organic pollutants. Concentrations of banned organochlorine pesticides as well as a number of current-use pesticides in samples from the first four years, roughly coinciding with 2005, 2006, 2007 and 2008, show distinct spatial and temporal patterns. Whereas organochlorine pesticides such as alpha- and gamma-hexachlorocyclohexane, endosulfans, DDT and its metabolites, and chlordane-related compounds tend to be more prevalent in developing countries, especially in Asia, concentrations of current use pesticides such as trifluralin and chlorothalonil are often higher in Europe and North America. Based on 15 stations with four years of data, levels of hexachlorobenzene, hexachlorocyclohexanes and chlordanes decline in most world regions, which may reflect decreased usage in response to global restrictions. Levels of organochlorine pesticides in India, however, remain exceptionally high. Concentrations of alpha-endosulfan, chlorothalonil and trifluralin decrease in the European atmosphere during the sampling periods, indicating reduced usage. Consistently high alpha/gamma-HCH ratios in air samples from high Northern latitudes confirm that re-volatilization from the Arctic Ocean is a significant source of alpha-HCH. The highest levels of alpha-HCH, however, occur in conjunction with high gamma-HCH levels, suggesting that lindane use is now the major source of alpha-HCH to the global atmosphere. Although a wide variety of sampling site types aids in characterizing the entire global concentration variability of a pesticide, it also increases greatly the number of sites required for a robust regional differentiation.

Levels of polycyclic aromatic hydrocarbons in Canadian mountain air and soil are controlled by proximity to roads

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in soil and XAD-based passive air samples taken from a total of 22 sites along three transects (Revelstoke, Yoho, and Observation, 6-8 sites for each transect) in the mountains of Western Canada in 2003-2004. Median concentrations in air (4-ring PAHs: 33 pg/m(3)) were very low and comparable to those in global background regions such as the Arctic. Low median soil concentrations (16 EPA PAHs: 16 ng/g dry weight) and compositional profiles dominated by naphthalene and phenanthrene are similar to those of tropical soils, indicative of remote regions influenced mostly by PAHs from traffic and small settlements. Comparing levels and composition of PAHs in soils between and along transects indeed suggests a clear relationship with proximity to local sources. Sampling sites that are closer to major traffic arteries and local settlements have higher soil concentrations and a higher relative abundance of heavier PAHs than truly remote sites at higher elevations. This remains the case when the variability in soil organic carbon content between sites is taken into account. Both air/soil concentration ratios and fugacity fractions suggest atmospheric net deposition of four-ring PAHs to soils.

Fate of pesticides in the arid subtropics, Botswana, Southern Africa.

Despite a history of pesticide usage, few data exist on their concentrations in air and soil of Southern Africa. To add to the understanding of the processes controlling the fate of organic contaminants in arid regions, the levels, spatial trends, and seasonal variability of pesticides were studied in air and soil from Botswana. XAD resin-based passive air samplers (PAS) were deployed at 15 sites across the country from May 2006 to May 2007. Soil samples were collected from the vicinity of nine of the PAS sampling sites. In addition, 27 24-h high-volume air samples were collected in Maun, at the southeastern edge of the Okavango Delta, every two weeks for one year. Levels of pesticides in PAS were low, with α-endosulfan and lindane being most abundant. Concentrations in soils were extremely low and only soils with high organic carbon contained notable amounts of dieldrin and traces of other pesticides. In particular, air and soil from the Okavango Delta had very low levels even though the area had repeatedly been sprayed with DDT and endosulfan in the past. Air samples from Eastern Botswana, where the majority of the population lives, contained higher levels. Higher air concentrations of α-endosulfan occurred during summer and higher HCB levels occurred in winter. This seasonality was related with neither minor seasonal changes in temperature nor hydrological seasonal events such as the rainy season or the flooding of the Okavango Delta. Thus, the observed spatial and seasonal patterns are more likely related to pesticide usage pattern than to environmental factors or historical use. High temperature and low organic matter content limit the uptake capacity of most subtropical soils for pesticides. No evidence was found that sorption to dry mineral matter plays a major role. Arid soils in subtropical regions are therefore neither a major reservoir of organic contaminants nor do they constitute a significant long-term source of pesticides to the atmosphere.

Application of XAD-resin based passive air samplers to assess local (roadside) and regional patterns of persistent organic pollutants

We used XAD-resin based passive air samplers (PAS) to measure atmospheric levels of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) at five ombrotrophic bogs in Eastern Canada. The aims of our study were to investigate the influence of local roads on contaminant levels in the bogs, to derive the regional pattern of atmospheric concentrations, and to assess the uncertainties of the method. Expanded uncertainties based on the duplicate PAS deployed at 24 sites were good for the PAHs, while the deployment period of approx. 100 days was too short to yield acceptable uncertainties for PCBs. The regional PAH distribution was in good agreement with the calculated source proximity of the sampled bogs. We conclude that XAD-resin based PAS deployed for comparatively short periods are well suited for measuring atmospheric concentrations of volatile PAHs, while in remote regions longer deployment is necessary for less volatile PAHs and for PCBs.

Current‐use pesticide transport to Costa Rica's high‐altitude tropical cloud forest

To gain insight into the atmospheric transport and deposition of organic contaminants in high-altitude forests in the humid tropics, pesticides were analyzed in air, water, and soil samples from Costa Rica. Passive samplers deployed across the country revealed annually averaged air concentrations of chlorothalonil, endosulfan, and pendimethalin that were higher in areas with intensive agricultural activities than in more remote areas. Atmospheric concentrations were particularly high in the intensively cultivated central valley. Only endosulfan and its degradation products were found in soils sampled along an altitudinal transect on the northern side of Volcano Turrialba, which is facing heavily cultivated coastal plains. Consistent with calculations of cold trapping in tropical mountains, concentrations of endosulfan sulfate increased with altitude. Pesticide levels in lake, creek, fog, and arboreal water samples from high-elevation cloud forests were generally below 10 ng · L(-1). Endosulfan sulfate was the most abundant pesticide in water, with concentrations ranging from 0.4 to 9.4 ng · L(-1). Its levels were highest in water sampled from bromeliads. Levels of total endosulfan in water are much lower than the reported median lethal concentration (LC50) value for acute toxicity of α-endosulfan to tadpoles. Although this suggests that the presence of pesticide might not have a direct impact on amphibian populations, the possibility of effects of chronic exposure to a mixture of substances cannot be excluded. Fog was relatively enriched in some of the analyzed pesticides, such as dacthal and chlorothalonil, and may constitute an important deposition pathway to high-altitude tropical cloud forest.