From coal to DDT: the history of the development of the pesticide DDT from synthetic dyes till Silent Spring.

The controversial pesticide DDT arose out of a number of practical and conceptual developments in science and industry during the nineteenth and twentieth centuries. Here we trace its story back to experiments involving the industrial by-product coal tar, proceed to the development of modern organic chemistry and the establishment of an advanced dye industry, and go on to chart the attempt to identify and synthesize chemicals capable of killing the insects involved in human and crop diseases. This paper argues that work on the chemistry of coal tar played a significant role in the history of DDT because it helped bring about the scientific ideas and the practical objectives that led chemists to embark on the search for pesticides. It concludes by examining the Swiss-German DDT production industry in the early 1940s and the subsequent condemnation of DDT by an environmental movement epitomized by Rachel Carson's Silent Spring.

Organochlorine contaminants in coastal marine ecosystems of southern Alaska: inferences from spatial patterns in blue mussels (Mytilus trossulus).

We measured the concentrations and chemical structures of persistent organochlorines (OCs) in blue mussels (Mytilus trossulus) from 44 sites across southwest and southeast Alaska in an effort to determine both the sources of these compounds and the extent to which this region might be contaminated. High PCB concentrations were detected at Amchitka, Adak, and Unalaska Islands (83, 430, and 2800µgkg(-1) dry weight, respectively) in the Aleutians with relatively low concentrations elsewhere (7.1-51µgkg(-1) dry weight). Heavy PCB congener profiles (indicative of localized point sources) characterized the high concentration sites whereas distinctly lighter congener profiles (indicative of atmospheric transport) characterized the lower concentration sites. Elevated PCB concentrations at Adak were restricted to a small area along the island's eastern shore, suggesting either limited dispersion or rapid dilution of these compounds. More uniform chlorinated pesticide concentrations among the collection sites suggests that these compounds are entering the Aleutian ecosystem from distant sources. Pesticide concentrations correlated significantly with seabird density across the islands we sampled, thus identifying biological transport as a delivery mechanism of these compounds to the Aleutian archipelago. Our findings do not implicate persistent organochlorines as a significant factor in the recent pinniped and sea otter population declines across southwest Alaska.

Persistent organic pollutants in the blood of free-ranging sea otters (Enhydra lutris ssp.) in Alaska and California.

As part of tagging and ecologic research efforts in 1997 and 1998, apparently healthy sea otters of four age-sex classes in six locations in Alaska and three in California were sampled for persistent organic pollutants (POPs) and other chemicals of ecologic or environmental concern (COECs). Published techniques for the detection of POPs (specifically ∑polychlorinated biphenyls [PCBs], ∑DDTs, ∑hexachlorocyclohexanes [HCHs], ∑polycyclic aromatic hydrocarbons [PAHs], ∑chlordanes [CHLs], hexachlorobenzene [HCB], dieldrin, and mirex) in the tissue of dead otters were modified for use with serum from live sea otters. Toxic equivalencies (TEQs) were calculated for POPs with proven bioactivity. Strong location effects were seen for most POPs and COECs; sea otters in California generally showed higher mean concentrations than those in Alaska. Differences in contaminant concentrations were detected among age and sex classes, with high levels frequently observed in subadults. Very high levels of ∑DDT were detected in male sea otters in Elkhorn Slough, California, where strong freshwater outflow from agricultural areas occurs seasonally. All contaminants except mirex differed among Alaskan locations; only ∑DDT, HCB, and chlorpyrifos differed within California. High levels of ∑PCB (particularly larger, more persistent congeners) were detected at two locations in Alaska where associations between elevated PCBs and military activity have been established, while higher PCB levels were found at all three locations in California where no point source of PCBs has been identified. Although POP and COEC concentrations in blood may be less likely to reflect total body burden, concentrations in blood of healthy animals may be more biologically relevant and less influenced by state of nutrition or perimortem factors than other tissues routinely sampled.

Contaminant-associated alteration of immune function in black-footed albatross (Phoebastria nigripes), a North Pacific predator.

Environmental pollution is ubiquitous and can pose a significant threat to wild populations through declines in fitness and population numbers. To elucidate the impact of marine pollution on a pelagic species, we assessed whether toxic contaminants accumulated in black-footed albatross (Phoebastria nigripes), a wide-ranging North Pacific predator, are correlated with altered physiological function. Blood samples from adult black-footed albatrosses on Midway Atoll, part of the Hawaiian (USA) archipelago, were analyzed for organochlorines (e.g., polychlorinated biphenyls [PCBs] and chlorinated pesticides), trace metals (silver, cadmium, tin, lead, chromium, nickel, copper, zinc, arsenic, selenium, and total mercury), and a sensitive physiological marker, peripheral white blood cell immune function (mitogen-induced lymphocyte proliferation and macrophage phagocytosis). We found a positive significant relationship between organochlorines, which were highly correlated within individual birds (p < 0.001, r > 0.80, Spearman correlation for all comparisons; PCBs, 160 +/- 60 ng/ml plasma [mean +/- standard deviation]; DDTs, 140 +/- 180 ng/ml plasma; chlordanes, 7.0 +/- 3.6 ng/ml plasma; hexachlorobenzene, 2.4 +/- 1.5 ng/ml plasma; n = 15) and increased lymphocyte proliferation (p = 0.020) as well as percentage lymphocytes (p = 0.033). Mercury was elevated in black-footed albatrosses (4,500 +/- 870 ng/ml whole blood, n = 15), and high mercury levels appeared to be associated (p = 0.017) with impaired macrophage phagocytosis. The associations we documented between multiple contaminant concentrations and immune function in endangered black-footed albatrosses provide some of the first evidence that albatrosses in the North Pacific may be affected by environmental contamination. Our results raise concern regarding detrimental health effects in pelagic predators exposed to persistent marine pollutants.

Albatross species demonstrate regional differences in North Pacific marine contamination.

Recent concern about negative effects on human health from elevated organochlorine and mercury concentrations in marine foods has highlighted the need to understand temporal and spatial patterns of marine pollution. Seabirds, long-lived pelagic predators with wide foraging ranges, can be used as indicators of regional contaminant patterns across large temporal and spatial scales. Here we evaluate contaminant levels, carbon and nitrogen stable isotope ratios, and satellite telemetry data from two sympatrically breeding North Pacific albatross species to demonstrate that (1) organochlorine and mercury contaminant levels are significantly higher in the California Current compared to levels in the high-latitude North Pacific and (2) levels of organochlorine contaminants in the North Pacific are increasing over time. Black-footed Albatrosses (Phoebastria nigripes) had 370-460% higher organochlorine (polychlorinated biphenyls [PCBs], dichlorodiphenyltrichloroethanes [DDTs]) and mercury body burdens than a closely related species, the Laysan Albatross (P. immutabilis), primarily due to regional segregation of their North Pacific foraging areas. PCBs (the sum of the individual PCB congeners analyzed) and DDE concentrations in both albatross species were 130-360% higher than concentrations measured a decade ago. Our results demonstrate dramatically high and increasing contaminant concentrations in the eastern North Pacific Ocean, a finding relevant to other marine predators, including humans.

Integrating life-history and reproductive success data to examine potential relationships with organochlorine compounds for bottlenose dolphins (Tursiops truncatus) in Sarasota Bay, Florida.

Research initiated in 1970 has identified a long-term, year-round resident community of about 140 bottlenose dolphins (Tursiops truncatus) in Sarasota Bay, Florida, providing unparalleled opportunities to investigate relationships between organochlorine contaminant residues and life-history and reproductive parameters. Many individual dolphins are identifiable and of known age, sex, and maternal lineage (< or =4 generations). Observational monitoring provides data on dolphin spatial and temporal occurrence, births and fates of calves, and birth-order. Capture-release operations conducted for veterinary examinations provide biological data and samples for life-history and contaminant residue measurement. Organochlorine concentrations in blubber and blood (plasma) can be examined relative to age, sex, lipid content, and birth-order. Reproductive success is evaluated through tracking of individual female lifetime calving success. For the current study, 47 blubber samples collected during June 2000 and 2001 were analyzed for PCB concentrations of 22 congeners relative to life-history factors and reproductive success. Prior to sexual maturity, males and females exhibited similar concentrations of about 15-50 ppm. Classical patterns of accumulation with age were identified in males, but not in females. Subsequently, males accumulated higher concentrations of PCBs through their lives (>100 ppm), whereas females begin to depurate with their first calf, reaching a balance between contaminant intake and lactational loss (<15 ppm). In primiparous females, PCB concentrations in blubber and plasma and the rates of first-born calf mortality were both high. First-born calves had higher concentrations than subsequent calves of similar age (>25 vs.<25 ppm). Maternal burdens were lower early in lactation and increased as calves approached nutritional independence. Empirical data were generally consistent with a published theoretical risk assessment and supported the need for incorporation of threats from indirect anthropogenic impacts such as environmental pollutants into species management plans. Long-term observational monitoring and periodic biological sampling provide a powerful, non-lethal approach to understanding relationships between organochlorine residue concentrations in tissues and reproductive parameters for coastal dolphins.

Surveillance for previously unmonitored organic contaminants in the San Francisco Estuary.

The San Francisco Estuary Regional Monitoring Program initiated surveillance monitoring to identify previously unmonitored synthetic organic contaminants in the San Francisco Estuary. Organic extracts of water samples were analyzed using gas chromatography-mass spectrometry in full scan mode. The major contaminant classes identified in the samples were fire retardants, pesticides, personal care product ingredients, and plasticizers. Evidence from the literature suggests that some of these contaminants can persist in the environment, induce toxicity, and accumulate in marine biota and in higher food chain consumers. The major sources of these contaminants into the marine environment are the discharge of municipal and industrial wastewater effluents, urban stormwater, and agricultural runoff. As a proactive effort, it is suggested that surveillance studies be used routinely in monitoring programs to identify and prevent potential problem contaminants from harming the marine environment.

An evaluation of the success of dredging as remediation at a DDT-contaminated site in San Francisco Bay, California, USA.

Lauritzen Canal, a portion of San Francisco Bay near Richmond, California, USA, was heavily contaminated with dichlorodiphenyltrichloroethane (DDT) and dieldrin as a result of releases from a pesticide-formulating firm. In 1996 and 1997, 82,000 m3 of contaminated sediment was removed from the canal by dredging. This study evaluated the success of the dredging based largely on body burdens of DDT and its metabolites (sigmaDDT) in resident biota, with some data on sediment- and water-contaminant levels and sediment toxicity testing. Sediment disturbance during dredging introduced a pulse of sigmaDDT into the Lauritzen Canal ecosystem, and body burdens of fish and invertebrates increased 2- to 76-fold, depending on the species. Approximately 1 1/2 years after remediation, 11 of 14 indicators showed contamination comparable with or worse than the contamination that existed prior to dredging. Monitoring of mussels up to four years postdredging suggests some modest improvement, although the sigmaDDT body burden of canal mussels remained far above the norm for San Francisco Bay. The elevated sigmaDDT body burdens in biota that persisted for years after remediation reflect recent exposure and are not merely a result of slow metabolic elimination of the sigmaDDT pulse associated with dredging. Sediment sigmaDDT concentrations were low immediately after dredging, but within months, the canal bottom became covered with a veneer of fine sediment as contaminated as that that had been removed. The source of this material has not been conclusively established, but we suspect it came from slumping and erosion from the flanks of the canal beneath docks and around pilings where dredging was not done. In retrospect, either capping in place or more thorough dredging may have been more successful in reducing pesticide exposure of the biota, although there were difficulties associated with both alternatives.

Man-made chemicals found in remote areas of the world: the experimental definition for POPs.

Members of the United Nations Economic Commission for Europe (UN-ECE) signed a legally binding protocol on persistent organic pollutants (POPs) in February 1998 under the Convention on Long-Range Transboundary Air Pollution. A treaty that intends to control the production, import, export, disposal and use of toxic chemicals that persist for decades in the environment has been formally signed at a conference in May 2001 in Stockholm. The 2001 POP treaty, like the 1998 LRTAP POP protocol, contains a provision on adding further chemicals to the initial group of twelve or fifteen. The occurrence of a compound or a group of compounds in so called remote and pristine areas, e.g. in the Artic or in the Southern Hemisphere, proves its stability under the chemical and biological conditions of the environment. Compounds identified in this way, in samples taken primarily in very remote regions of the planet, are classified by their environmental fate and global distribution as persistent organic pollutants (POPs), regardless of any political assessments.