FROGS in an EFFLUENT SOCIETY Risks, Remedies and Responsibilities by Dr Sara Broomhall First Published in June 2004 by WWF Australia © WWF Australia 2004

Author: Dr Sara Broomhall

WWF Australia GPO Box 528 Sydney NSW Australia Tel: +612 9281 5515 Fax: +612 9281 1060 www.wwf.org.au

For copies of this booklet or a full list of WWF Australia publications on a wide range of conservation issues, please contact us on [email protected] or call 1800 032 551.

The opinions expressed in this publication are those of the authors and do not necessarily reflect the views of WWF.

Special thanks to Craig Cleeland for supplying the photographs for this booklet. CONTENTS

FROGS AS ENVIRONMENTAL BAROMETERS The aim of this booklet is to help What is a pollutant? 2 you understand: Australian frogs 2 How do frogs interact with their environment? 3 What pollutants are – Life stages 3 – Habitat requirements 3 How frogs interact with their environment – Ecological position 3 – Frogs and pollutants in the food chain 3 Why water pollution affects frogs Why is environmental pollution a frog issue? 3 – Are frogs more sensitive to environmental pollutants than other species? 3 Where pollutants come from and how they enter the environment WHAT WE DO AND DON’T KNOW Why don’t we have all the answers? 4 How you may be polluting water – How relevant are these toxicity tests to real world situations anyway? 4 Categories of pollutants (such as pesticides) Where do pollutants come from? 4 How many chemicals do we use here in Australia? 4 and their effects on frogs Who produces pollutants? 4 Where you can go for further information WHAT’S HAPPENING? So how am I polluting? 6 What alternatives there are and Let’s take a ride through the wastewater system 6 what products you can substitute – The ins and outs of waste water 7 What do we know about agricultural pesticides and where they go? 8

THE USUAL SUSPECTS What can we really say about the effects that all the chemicals we use have on Australian Frogs? 9 – Pesticides 9 Organochlorines 9 Organophosphates 9 Carbamates 9 – Herbicides and fungicides 9 – Surfactants 10 – Additives 10 – Endocrine disrupting chemicals 10 – Fertilisers 10 – Combinations 10 – Metabolites 11

TAKING ACTION Where can I find out about these chemicals? 11 So what can you do? 12 – What can you do with leftover hazardous household products or pesticides? 13 – Some alternative suggestions 13 1 FROGS AS ENVIRONMENTAL BAROMETERS

What is a pollutant? Australian frogs Pollutants are potentially harmful, Australia really is a lucky country – we have and sometimes lethal. It’s easy to think of more than 210 species of frogs! What is more, chemicals such as pesticides, detergents, because Australia has been isolated from industrial chemicals and so forth as pollutants. other land-masses for so long, our frog species Less obvious examples might be extremely are quite different from the species found high nitrogen or phosphorus levels in water in other countries. In Australia, we have due to fertiliser runoff and sewerage discharges, three main native frog families. They are the or sediment from cleared lands. Salinity and Myobatrachidae (or ground frogs), the Hylidae litter also cause pollution problems. (tree frogs), and the tropical Microhylidae. For the purposes of this booklet, our main emphasis is water-borne pollutants - those readily identifiable culprits such as pesticides, household detergents, assorted chemicals, and fertilisers.

Pesticides are substances (or mixtures of substances) that are intended to prevent, kill, or repel a particular pest. ‘Pests’ are species that we want to get rid of, for any number of reasons. Pests can include insects, mice and other animals, unwanted plants (weeds), fungi, or microorganisms like bacteria and viruses. The term ‘pesticide’ therefore also includes herbicides and fungicides. Unfortunately, most pesticides have some risk of harm to non-pest species precisely because they are designed to be harmful. Of course, many things can be toxic in high enough amounts, even caffeine and parsley, but such high amounts are very unlikely to occur. Problems arise when the amounts we use regularly are directly harmful, or accumulate to harmful concentrations in nature.

2 How do frogs interact with Ecological position Why is environmental their environment? Frogs are important components of many pollution a frog issue? ecological communities, consuming vast Life stages amounts of invertebrates and, in turn, providing The skin of a frog is very permeable. The Frogs generally start their life cycle as eggs an abundant food source for many other tadpole stage also relies on gills for breathing. encased in jelly capsules. Depending on the predators, such as birds and snakes. Both of these physiological characteristics make species, the eggs develop on land or in water. frogs and tadpoles very susceptible to a number Frogs and pollutants in the food chain They gradually turn into tadpoles, hatch, and of contaminants, which often easily penetrate If pollutants affect frogs, this can then have become free-swimming. Tadpoles breathe via exposed surfaces such as gills and skin. carry-on effects on the ecological community. gills, like fish. They continue to grow until they Pollutants that may not be easily excreted Consequently, because frogs inhabit water and reach a certain stage, when a complex hormonal or broken down by the body, can accumulate in land, they may have more opportunities to be process kicks in that changes them into frogs. body tissues. This is known as ‘bioaccumulation’. exposed to environmental contaminants than This is called ‘metamorphosis’, and it is really When these animals or insects are then many other animals. Frogs also have more ways quite remarkable. When they crawl out onto consumed by another animal, the toxins in the of being exposed than other animals, because land, the frogs are then mostly terrestrial and prey can then accumulate in the predator’s they have gills as tadpoles and a very permeable breathe via their skin and the back of their body. This process is called ‘biomagnification’. skin as an adult. throat. Frogs have an essentially "naked" egg After eating a few contaminated prey items, (it doesn’t have a shell) and, along with other Frog limb abnormalities have been proposed the concentrations of toxins in the body of amphibians such as salamanders and caecilians as a possible indicator of environmental top predators can become extremely high. (neither of which are native to Australia), are the abnormalities, particularly in agricultural areas. Frogs can bioaccumulate toxins by ingesting only vertebrate group that has both an aquatic However, deformed frogs are rare in Australia. contaminated insects and also through direct and terrestrial phase. exposure to pollutants, particularly in the water. Are frogs more sensitive to environmental Habitat requirements When frogs are killed by these pollutants, either pollutants than other species? Frogs need an environment that is moist, directly, or because the pollutants make them Yes and no. In some situations, and for some because they ‘drink’ and breathe through very sick and unable to escape a predator, then toxins, frogs may be particularly susceptible their skin. Most species lay their eggs in water, this causes problems all the way up the food to contamination. For example, the insecticide so the availability of water is essential. Some chain. Frogs, with their toxic payload, may make endosulfan is ten times more toxic to Rana frogs have evolved to take advantage of the animals that eat them very sick. With fewer tadpoles than to catfish or damselfly nymphs. temporary pools of water that are created frogs to eat insects, there are ecological We rarely test the effects various contaminants by heavy rain. Others lay their eggs in rivers, problems down the food chain as well. have on adult frogs so in many cases, we and yet others congregate around permanent simply don’t know how sensitive they are. ponds and streams. Unfortunately, there is not enough research to provide a definitive answer to this question for most frog species.

3 WHAT WE DO AND DON’T KNOW

Why don’t we have all Where do pollutants Who produces pollutants? the answers? come from? The list of who produces pollutants is We are blessed with lots of frog species, Outside of natural disasters, almost all enormous because many things that we use in but environmental toxicology is a relatively new pollutants are the result of human activities, day to day life either cause pollution while being field here in Australia. The majority of aquatic whether created directly, or as by-products manufactured, or become a pollutant when toxicological testing usually focuses on species of production processes. we finish with them. such as fish, shrimp, and invertebrates. Take, for example, most peoples’ morning routine. How applicable are studies on fish and How many chemicals do we use here in Australia? You get out of bed. If it’s a wooden invertebrates to frogs? Good question!! bed, the wood has usually been treated with Generalisations are hard to make because a For a start, there are over 40,000 industrial preservatives and anti-fungal agents, perhaps frog’s sensitivity also varies according to the chemicals listed by regulatory authorities, and sealed with a varnish. Many of these treatment specific toxin tested. For example, we know that over 4,500 agricultural and 3,000 veterinary processes discharge waste water, not to frogs do not react to mercury the same way fish products registered for use in Australia. Do we mention the initial process to produce the do. Consequently, we cannot assume that frogs know the effects that each of these chemicals preservatives and varnishes, all of which are will react the same way as other animals – or have? Frogs are not a standard test species, so likely to be toxic to frogs in variable amounts. even that all species of frogs will react the in most cases we don't know what they do to Chlorinated phenols are used as wood same. However, frogs are more similar to frogs. In addition, many chemical formulations preservatives and pesticides, and are often fish in many ways than they are to birds are based on other, older formulations. These the by-products of paper pulp milling. All these and mammals. formulations have generally been originally chemicals are toxic in high doses. tested a long time ago and so may not meet At least 80% of the available research If the sheets on the bed are cotton, they contemporary standards. The Australian have usually undergone a bleaching and dying on environmental contaminants and Pesticides & Veterinary Medicines Authority process. Chlorine based bleaches can be frogs uses American and European (APVMA) assesses existing chemicals in dangerous to frogs. The cotton industry uses response to concerns about their health, species. Unfortunately, these studies thousands of tonnes of insecticides every year trade or environmental effects. may have little direct relevance to control pests. Pesticides, and their effects to the unique frog species and Due to the huge number of chemicals in use, on frogs, are discussed in much greater environmental conditions in Australia. only a small proportion have been assessed detail later on in this booklet. Your sheets are and so we often don't know the effects that all partially polyester? Many plastics industries In many cases, we don’t know what chemicals these chemicals have on frogs. are again highly polluting. Bisphenol A, a high- are, or might be, in our waterways. We also volume chemical used to make polycarbonate Unfortunately, information on agricultural don’t know if or how they may combine to form plastic, epoxy resins, and other chemicals, has and veterinary chemical usage is not formally new toxins. Nor do we know what they may been shown to be weakly estrogenic to fish. collected across Australia. We do know that break down into. Estrogen is an important hormone that regulates herbicides, insecticides and fungicides have many bodily functions in many animals, How relevant are these toxicity tests to been regularly used in Australian farming for including frogs. real world situations anyway? at least 40 years. We also know that all forms One of the most widespread protocols for of pesticide use have increased over the past Polychlorinated biphenyls (PCBs), which are assessing the toxicity of a chemical to an two decades and that we spend around a billion widespread contaminants in industrialized aquatic species is the acute toxicity test, dollars on them annually. nations, were used to manufacture paints, which provides information about what sort of plastics, adhesives and electrical goods (such concentrations are overtly harmful to the test as transformers and capacitors), non-carbon animals. However, even though animals may not copying paper and are used as hydraulic and die, they may get sick, or their growth may be cooling fluids. PCBs have been shown to stunted. Such chronic effects appear only after cause reproductive failure in birds, cause liver, weeks, months or years, and are much more stomach and thyroid gland injuries and affect difficult, and costly, to assess. Bacteria and light the immune system in other animals. PCBs are can break down some chemicals into other so persistent and mobile in the environment that substances and these may be more or less almost everyone has been exposed to them. harmful than the original compound.

4 You grab your towel (again it is likely to be hatchlings, and development in tadpoles. cotton) and walk across to the bathroom. Your antiperspirant contains aluminium, which Think about the preserved and sealed wood may have effects on the nervous system, and is of the floor, and how logging industries can toxic to frogs at concentrations of 0.86 - 1.6 mg/L. also cause problems with erosion and sediment Your toothpaste can contain carrageenen as a into rivers. The rug on the floor and the paint thickener, triclosan as an antibacterial, and on the wall may be a source of acrylic acid. fluoride. The first can cause intestinal ulcerations, This acid is used to produce acrylic esters the second has been shown to accumulate in wild and resins, and used in detergent intermediates fish, and there is some evidence that fluoride- and oil treatment chemicals. It is also emitted contaminated water can cause frog eggs to hatch in the production of acrylate, and from polishes, prematurely. We don’t know what effects these paints, coatings, rug backings, adhesives, things have on Australian frogs. plastics, textiles and paper finishes. According to the National Pollutant Inventory database All of these products are washed down the (collated by the Department of Environment drain. Many trillions of litres of contaminated and Heritage DEH), about 90% of acrylic acid in water flows through sewerage systems in the environment is expected to end up in water. Australia every day. Although sewerage is It has slight toxicity to aquatic organisms such partially treated, treatment plants often do not as fish and has high toxicity to birds. capture all the solids we rountinely flush down toilets, such as wrappers, cigarette butts, dental In the bathroom, you step into the shower. floss, nappies, and toilet paper, let alone treat Your shampoo bottle is usually made from things like chemicals, cleaning products plastic. Its label is usually bleached paper and detergents. (as is most toilet paper). Pulp and paper mills discharge dioxins to air and billions of liters At least 80% of water samples taken from rivers of liquid effluent each year. In fish, this effluent and catchments in the USA in 1999 and 2000 can cause delays in sexual maturity and reduced contained chemicals such as disinfectants, egg production, depress sex steroids, cause antibiotics, antioxidants, caffeine, fire- masculinisation of female fish, and suppress retardants, and fragrances. Surfactants immune functions. and platicizers (such as 4-nonylphenol and bisphenol-A) were also found in over 50% Your shampoo may contain up to 50 of samples. The potential toxicological effects ingredients. A number of them are foaming of most of these compounds are relatively agents, or ‘surfactants’. Surfactants have been unknown. This means that many possible shown to be harmful to frogs and are discussed contaminants are entering our waterways, and more extensively later on in this booklet, on we simply do not know what effects they may page 10. Some anti-dandruff shampoos contain have on our frogs. Research has shown that selenium. Excess selenium is associated with caffeine is teratogenic (i.e. causes birth defects) reproductive effects and mortality in wild birds, to the African clawed frog (Xenopus laevis) although we don’t have a good understanding and causes malformations of embryos at of what it does to frogs. However, sodium concentrations of 0.12 mg/L. One cup of coffee selenite has been shown to cause severe contains 100mg caffeine. Interestingly, caffeine developmental abnormalities in the African spray is now being used as a slug and snail clawed frog (Xenopus laevis) at concentrations killer; and may also be used to control pest of 2 mg/L. One teaspoon of salt is 5,000 mg, frogs in Hawaii, by causing then to go into so 2mg is a very tiny amount. cardiac failure. Your shaving cream may contain We haven’t even gotten to electricity, or your octylphenol, which is also a breakdown morning coffee, or breakfast, or cars, or roads product of a chemical widely used in the pulp and yet! This is meant to illustrate how things that paper industry and is found in many common are either directly polluting, or are the result household cleaners. Octylphenol adversely of an industry that pollutes, permeate our affects both the growth of snapping turtle daily lives.

5 WHAT’S HAPPENING?

So how am I polluting? as cigarette butts, bandage wrappers and cotton passing through, nor what effects they might tips (which slip through traps and filters), have. The presence of many potential Potential sources of pollution in a city or pesticides, and poisons are being tipped contaminants are not routinely monitored. For town include: down the drain. When compared to 1994, example, domestic inputs to sewerage works i. domestic pesticide use an additional 2,174 tonnes of grease and oil contain natural and synthetic estrogens from ii. domestic fertiliser use entered the system in 2001. The Minister human excretion, such as estradiol. Very small iii. discharge from sewerage treatment responsible for Sydney Water cautioned that concentrations of estradiol have been shown plants (both domestic and industrial many of these items may cause blockages in to cause many developing African clawed frog sources) pipes, causing them to overflow, and smaller (Xenopus laevis) embryos to become female. iv. transport of pollutants and sediments items slip through screens and can end up Estrogens in the environment, or chemicals that via stormwater directly in waterways. Chemicals and poisons mimic oestrogens, are thought to disrupt many v. irrigation drainage and runoff can’t be screened and are difficult to treat, hormonal processes in aquatic animals. from roads they too can end up in our waterways. Chemicals that do this are known as ‘Endocrine Disrupting Chemicals’ (EDCs), and are vi. groundwater contamination from The responsibility lies with all of us. discussed more comprehensively later on. land fills. We cannot rely on the sewerage system to take i.& ii. Domestic pesticide and fertiliser use: care of the household items we put down the Effluent and receiving waters around Sydney Many household products are classified as drain. Everything we do may directly affect our sewerage treatment plants (STPs) have been pesticides. Did you know that insect repellents; waterways and the frogs that live in them. found to contain significant amounts of metals flea and tick sprays, powders, and pet collars; We need to be mindful of what we do – such as boron, cadmium, cobalt, copper cockroach sprays and baits; rat and mice in some cases it may be easy to change (which causes gastrointestinal, liver and kidney poisons; some kitchen, laundry and bath a behaviour. For example, one could pour old problems in humans, and disrupts gill function disinfectants and sanitizers; mold and mildew milk onto a garden bed, not down the drain in fish), silver, iron, lead (which can delay mental killers; some lawn and garden products (such (milk can clog up the treatment system). And development in humans and cause kidney as weed killers); and some swimming pool old paints and garden sprays can be taken to problems), mercury, manganese and nickel. chemicals are classified as pesticides? chemical disposals. There are suggestions and Many heavy metals are acutely toxic to fish and details on where one can safely dispose frogs. For example, cadmium causes mortality Did you know that some flea powders, of old chemicals at the end of this booklet. in a salamander, Ambystoma opacum, collars, and sprays may include carbamates, at concentrations above 10.2 µg/L. A teaspoon pyrethrins, chlorpyrifos, and organophosphates? Let’s take a ride through the of salt is about 5 million µg (not including the If you have never heard of these chemicals, wastewater system… spoon, of course!), so 10 µg (called"micrograms"), then perhaps now is a great chance to start is about as much as a single grain of salt in a learning about them. I will define pesticides Sewerage: litre of water. Metals are heavier than salt, so the and their effects further on. Fertilisers can Sydney Water provides sewerage services amount we are talking about here is very, very, contain heavy metals or change soil pH, to collect, transport and treat wastewater from very tiny. or cause excess nutrients in waterways that households and industry, for more than may lead to algal blooms. 3.9 million people. This equates to around The maximum concentrations of aluminium 1,300 megalitres (a megalitre is one million in effluent and receiving waters at Blackheath, iii. Discharge from sewerage litres) of wastewater every day! I mention NSW over the past six years ranged between treatment plants: Sydney Water only in order to illustrate how 110 µg/L and 1,420 µg/L. These are 2 to 25 Many people flush things down the drain sewerage systems operate in Australia, and times the trigger value of the Australian and because its an easy way to get rid of them. because so many Australians live in Sydney. New Zealand Water Quality Guidelines, and In 2000-2001 Sydney Water collected 1,348 Sydney Water also provides good information therefore likely to be harmful to organisms cubic metres of litter from the litter booms, services, so we can get a better picture of such as tadpoles that inhabit these waters. trash racks and gross pollutant traps. what happens. Aluminium is toxic to the American toad Sediment capture was almost 40,000 tonnes. (Bufo americanus) at concentrations between This, however, is less than 70% of the solids We already know that sewerage treatment 860-1,660 µg/L. Remember that a teaspoon that flow through the system. plants do not eliminate all harmful contaminants of salt is about 5 million µg, so this is less flowing through the system. For example, many A Sydney Water media release titled "Household than 1/3,000 of a teaspoon! plants exhibit leaf damage when irrigated with Sinks Put Environment at Risk" on 02 May 2002 'reuse' water, which is sewerage water that has STP discharges have also been found to contain cautioned that increasing amounts of paints, had partial treatment but is not yet drinkable. cyanide (which disrupts respiratory functions solvents, paint strippers, fuel, oil, food scraps, What we don’t know is exactly what things are in animals), chlorpyrifos (an organophosphate milk, cooking oil, small rubbish items such insecticide), dieldrin (an organochlorine

6 The in’s and out’s of waste water

solids milk detergents No tests for some contaminants paint High Volumes (eg. 1,300,000,000 L per day in Sydney) cleaning products pesticides etc. incinerators - dioxins

ash & soil conditioners input to drains, toilets etc. - heavy metals ground water - pH

Solid Output

changes in vegetation Sewerage Treatment Plants irrigation

Liquid Output ground water by-pass heavy metals - aluminium storm water - chromium - boron - mercury to streams etc. - lead road debris pesticides oil caffeine detergents painkillers weedkillers benzene petrol etc. surfactants urea hormones chlorine nitrate

7 insecticide), chloramines, and nonyl phenol What do we know about ethoxylates (surfactants). agricultural pesticides and Residual chlorine (used to disinfect drinking where they go? water and sewerage, also contained in many Although agriculture is the largest user of home disinfectants) has been detected in the pesticides, significant quantities of herbicides effluent and receiving waters of Sydney STPs are also used by local councils and road and rail for several years. The observed maximum authorities for weed control. concentration in the effluent and receiving Run-off occurs when chemicals have been waters at Castle Hill, NSW during 1999/2000 applied to plants and then water (either rain We do not know the total contaminant load was 2,230 mg/L – a total load of 1,829.28 kg or irrigation) washes these chemicals off the in Australia - how much is used and where in one year. This value is double or triple the plants, and either into the soil or off into dams, it is used -we can only make estimates based concentration that kills fish, because chlorine is creeks and rivers. on the amount of money spent per year. toxic to freshwater fish at concentrations of 70- vi. Groundwater contamination from The problem with estimates is their uncertainty. 840 µg/L. Many sewerage treatment places such landfills and industrial activities: Chemicals may break down or degrade, and as Sydney water are committed to improving ‘Groundwater’ is the underground reservoir these degradation products may act in many water quality around discharge sites. But it is that supplies wells, springs, and creeks. different and unpredictable ways. Chemicals a big and expensive job. It provides around 20% of Australia’s total can also move off-target. Refer to diagram below. For example, 1) those which are sprayed It is highly unlikely that discharges will ever be water requirements; this figure increases can move through the air, 2) those applied harmless. Therefore, it is up to all of us to be to 100% in some remote mining settlements. directly to the soil may be washed off into mindful of what we add to this toxic burden on Deep below ground, it may still become nearby surface water, or 3) they may percolate our waterways. We can all help frogs by not contaminated by agricultural and industrial through the soil to groundwater, 4) groundwater putting harmful things down the drain. activities. Even your own backyard has the can also transport chemicals into surface water iv. Transport of pollutants and sediments potential to affect groundwater in surrounding bodies or irrigation water sources elsewhere, via stormwater areas. Agricultural dip-sites (especially where and 5) sediment can be an additional potential The litter you throw in the streets, the oil your arsenic and organochlorine products were source of exposure. Lastly, the potential effects car drips onto the road, and the soap suds you used), old metal smelting sites (such as copper of exposure to multiple pesticides applied in a wash off your car can all make it through the and lead), closed tips, gas plants and works, given area cannot be assessed. stormwater drains and into your local river. garages, power stations (where buried hydrocarbons and heavy metals occur), So now that I have talked about the numbers A secondary consequence of stormwater is that manufacturing spills, broken pipelines, and and volumes of chemicals we use ourselves, at times of higher flows (such as during intense mining-related activities and bores are all sites how can we tell what effects these may have rainfall) the capacity of STPs to treat and where contaminants can leach through the soil on frogs? manage wastewater becomes weakened, and to groundwater unless responsibly managed. thus flows bypass some treatment processes. Consequently, partially treated sewerage can be discharged directly into rivers. Such discharges can generate an acute pollution episode. An example of this is the 300 tonnes of dead wind volatilization fish removed from a river in France after a photodegradation storm event in 1992. v. Irrigation drainage ‘Spray-drift’ and ‘run-off’ are terms that describe when contaminants move away from runoff the place where they were intended. Chemical sprays, particularly fine ones, can be blown plant uptake Sorption to a long distance by the wind. This can cause soil particles serious problems in agricultural operations where spray is released from aeroplanes or big machinery, but it can also be a problem in your Leach to groundwater microbial or own backyard if you spray on a windy day. chemical degradation

8 THE USUAL SUSPECTS

What can we really say final section is a special case of compounds that most Sydney STPs. The observed maximum about the effects that all the have particular action. These are the endocrine concentration of diazinon was 1.71 µg/L. Little disrupting chemicals. information is available on the effects of chemicals we use have on diazinon on frogs. As an illustration, a search Organochlorines Australian frogs? of a scientific journal database produced 1,553 Organochlorines were the first synthetic papers that mentioned diazinon. Only one Unfortunately, the answer is: we can say very chemical pest control agents, and include DDT, of these was on frogs. This paper, a Canadian little. Existing research suggests that many chlordane, lindane, endosulfan, metolachlor, study, found that the lethal concentration products have the potential to be harmful, but in pronamide and heptachlor. DDT was used of diazinon to green frogs (Rana clamitans) most cases we simply don’t know. We are extensively in developed nations until it was was 2.8 to 5 µg/L. forced to make educated guesses. banned from use in the USA in 1972 and I have listed three main categories of Australia in the mid 1980's, although it is still Therefore, we don’t know their potential risks contaminants: widely used in much of the rest of the world. to Australian frogs.

Pesticides, DDT, and most other organochlorines, have very Carbamates Surfactants (detergents, soaps, high environmental persistence. For example, a Like organophosphates, the low persistence wetting agents, and their metabolites) recent study found that the average residue of carbamate insecticides has led to their levels of DDT in the stomach contents of birds widespread acceptance. Carbamates often and adhesives in Australia in 1990 were 179.21 µg/L (a µg is disrupt the movement of nerve impulses. Fertilisers and heavy metals. one millionth of a gram) despite not being used Despite their acceptance, carbamate based This list is by no means comprehensive, and for 20 years. Harmful effects have been reported insecticides have been found to produce many compounds and their effects simply in one frog species at concentrations as low as developmental malformations in skeletal cannot be included here (unless you really want 2 µg/L DDT. This amount is equivalent to two tissue and musculature of Rana species. to read a tome the size of the Sydney telephone pinches of salt in ten tons of potato chips. Exposure of Xenopus laevis and Hyla tadpoles directory!). The idea here is to introduce you to to carbaryl caused mortality at some Organochlorine residues continue to be detected the sorts of things that are commonly used and concentrations and changed swimming in fish from the Mississippi River Basin. some of the possible effects they can have. behaviour at others. In addition, its toxicity Organochlorine pesticides such as endosulfan Pesticides: increased tenfold in the presence of are still being used in Australia. Endosulfan ultraviolet-B radiation. There are currently over 4,500 agricultural attacks the central nervous system in mammals, pesticide products registered for use in We can assume the effects on Australian but we don’t know what it does to frogs. Australia. These products are used extensively species are likely to be similar, but until formal in both urban and rural environments. Any given Organochlorines such as dieldrin, endosulfan, studies are conducted, the real dangers remain active ingredient can be used in many different toxaphene, and chlordane are also weakly virtually unknown. brands and formulations. For example, the estrogenic (they act as hormone mimics). Herbicides and fungicides: herbicide 2,4-D has over 100 trade names Endocrine disrupting chemicals have been Atrazine is the most commonly used herbicide and formulations. shown to cause extensive limb malformations in in the U.S. In Australia, atrazine has been found the frogs Rana clamitans and Rana catesbeiana. When used according to label directions, many to contaminate as much as 50% of groundwater Despite widespread contamination, very few pesticides should be relatively safe for humans, samples in some areas, although the extent of studies have measured organochlorine residues However, again, we are generally unsure what groundwater testing is extremely limited. in native Australian frogs. effects they have on frogs. Moreover, when Recent research has found that male African they move off target, breakdown or accumulate Organophosphates clawed frogs (Xenopus laevis) suffered a tenfold in water bodies, then their effects may be Today, organophosphates have partially decrease in testosterone levels when exposed to much worse. replaced organochlorines because of their lower 25 ppb (parts per billion) atrazine. One part per environmental persistence. Organophosphates Since the term ‘pesticide’ incorporates many billion is the equivalent of one drop of impurity tend to inhibit cholinesterase, disrupt enzyme products such as insecticides and herbicides, I in 500 barrels of water. Paraquat has been processes and nerve impulses, or denature have split the topic into six sub-sections which found to cause malformations to Xenopus laevis proteins. In Australia, we use them extensively can be read in any order. Three subsections embryos at concentrations of 0.2 mg/L. The in agriculture and within urban areas. discuss some of the major types of insecticides: fungicide Vinclozolin alters sex differentiation the organochlorines; the organophosphates; and The organophosphate pesticides diazinon and of male rats. Again, we do not know the effects the carbamates. The next three subsections will chlorpyrifos are active ingredients in a number of atrazine, or many other herbicides, on briefly outline herbicides, then additives, and the of domestic garden pesticides and both have Australia frogs. been detected in effluent and receiving waters in

9 Surfactants: Endocrine disrupting chemicals: Australian frogs have evolved in an environment Synthetic surfactants can also contribute to Many environmental contaminants, such as that is comparatively low in nitrate and water pollution, as around 7 million tons are plasticizers and pharmaceuticals, are known phosphate, so it is possible that Australian produced worldwide every year. Surfactants to have estrogenic effects, or behave as frogs may have a greater sensitivity to these are used in many compounds to break down hormone mimics or disruptors. These chemicals. Nitrates are becoming a larger the surface tension in water, and help them ultimately affect basic life functions such as concern among environmental monitoring disperse. Alkylphenols and alkylphenol growth, reproduction and development, and agencies in Australia because nitrate ethoxylates (APEs) are commonly used in maintenance of the body. Without killing contamination is considered the most significant many industrial, agricultural and domestic individuals, they can seriously jeopardise and widespread contaminant of groundwater. applications. Both of the surfactants alcohol whole populations. The main problem with increased nitrate ethoxylate and alcohol ethoxy sulfate were concentrations is the potential to stimulate While DDT is one such compound, the found to have toxic effects on Xenopus laevis algal growth and blooms. At high enough alkylphenolic surfactants used in items such embryos and tadpoles. In particular, embryos concentrations, nitrate is toxic to aquatic life. as detergents, paints and pesticides may be of had malformed gills. These two surfactants are greater concern. These chemicals are also used In temperate areas in south eastern South used extensively in consumer products. in industries including pulp and paper, textiles, Australia, dairies, piggery feedlots, cheese It appears that alkylphenols were not tested for pesticides, metals and plastics, and institutional factories, abattoirs, and spreading of wastes, in effluent of STPs here in Australia until last and household cleansers. For example, a nitrogenous fertilisers and natural leaching year. Nevertheless, nonyl phenol ethoxylates concentration of 16 µg/L Bisphenol A of leguminous fertilisers can greatly increase were detected in effluent and receiving waters (a high-volume chemical used to make concentrations of nitrate in groundwater. at Blackheath in 2000/2001. Although sewerage polycarbonate plastic, epoxy resins, and other Sugarcane growing is a major source of nitrate works treat effluent, they are not yet effective chemicals), altered the proportion of sex cell contamination in groundwater in coastal at removing many contaminants. types in the testis of male fish, while higher Queensland. Indeed, increased nutrient load concentrations inhibited gonadal growth in both is already affecting the Great Barrier Reef. Additives: sexes of fish. Remember than a microgram We tend to know formulations only by their Fertilisers can also dramatically change soil is one millionth of a gram. Bisphenol A also active ingredient, with little regard to the many chemistry, such as pH, and heavy metal content. bioconcentrates in freshwater clams and lower other additives that are not listed on the label. Acidity can also lead to mobilisation of metals water temperatures causes it to persist even such as aluminium & iron and can increase Here in Australia, Dr. Reinier Mann undertook longer in tissues. chemical demand for dissolved oxygen in research on glyphosate. Glyphosate is supposed A high incidence of intersexuality has been waterways, leading to lower oxygen availability to be one of the most non-toxic herbicides observed in wild populations of riverine fish in for fish and tadpoles. pH also alters how available. Dr. Mann found that the surfactant, many parts of the United Kingdom – this sexual tadpoles react to fungal attack, bacterial not the active ingredient, had serious impacts disruption is associated with exposure to infection, or how they are affected by heavy on frogs and tadpoles; therefore, compounds effluents from sewerage treatment works. metals or UV-B radiation, and so on. considered safe may not be safe at all. These sorts of findings can lead to companies Again, the effect of endocrine disrupting Many fertilisers contain impurities such as changing the formulations of their products, chemicals has not yet been studied in cadmium, lead and mercury. Most heavy metals however, such harmful effects are simply Australian frogs. such as mercury, boron, cadmium and cobolt unknown until someone does research are harmful to frogs. Mercury, for example, is Fertilisers: on it. Unfortunately, the amount of money one of the most toxic compounds to frogs yet Fertilisers have only recently been proposed spent on such research is vanishingly small. found. This means that fertilisers may have as a potential threat to frogs, but it is one considerable long-term impacts on our frog of the most serious problems at a local level. species; either directly, or through modifying Researchers in the northern hemisphere other variables such as pH and metal impurities. noted a correlation between amphibian declines and environmental increases Combinations: in nitrates and ammonia. Commercial preparations are often a combination of two or more pesticides Sublethal concentrations of nitrite in water or they incorporate various solvents, carriers caused both physical and behavioural or surfactants. Biological testing is generally changes in the Cascades frog in the USA. only done on the active ingredients. Urea fertiliser decreased survival in two American amphibian species.

10 TAKING ACTION

Some chemical combinations may have additive Where can I find out about Australian Water Resources Assessment 2000: or synergistic effects, that is, the combined these chemicals? audit.deh.gov.au/ANRA/water/docs/national/ effect is much greater than just the sum Water_Contents.html of the effects that each compound has by There are a number of handbooks available, Waterwatch : itself. They may also combine with other such as “The Pesticide Manual”, edited by www.waterwatch.org.au/ environmental parameters such as pH. CDS Tomlin and published by the British - ACT: www.act.waterwatch.org.au/ Crop Protection Council (2000), and “The Although little is known about interactive Agrochemicals Handbook”, edited by Kidd & - Vic: www.vic.waterwatch.org.au/ effects, the potential implications of James (1991), and published by The Royal contaminant mixtures are serious. - QLD: www.qld.waterwatch.org.au/ Society of Chemistry, Information Services, Metabolites: Cambridge, England. It lists many pesticides, - Tas: www.tased.edu.au/tasonline/dorsetww/ We also need to consider that chemicals break their chemical composition, and toxicology - NT: www.lpe.nt.gov.au/waterwatch/ down in the natural environment. Methoprene, data on various test species, but such - WA: www.wrc.wa.gov.au/ribbons/index.html used for controlling mosquitoes and fire ants, technical handbooks are big and heavy is considered comparatively safe and inert. Its and sometimes expensive. Sydney Water: an insect growth regulator that interferes with www.sydneywater.com.au Or you can contact agencies such as the insect development. Such biologically-based Environmental Protection Agency and Land & Water Australia: pesticides, or others that utilise pheromones the APVMA. www.lwa.gov.au and microorganisms, are becoming increasingly Australasian Society for Ecotoxicology: popular because they are often considered safer Probably your best bet is the world-wide-web. www.ecotox.org.au than traditional chemical pesticides. Quite a lot of information is readily accessible on various toxicology websites. However, be Food Standards Australia New Zealand: However, the photoproducts and metabolites warned that not all of the information on the www.foodstandards.gov.au/aboutus/ of methoprene, which form as it breaks web is scientifically based and can make down in sunlight, have been found to cause Other: unsubstantiated claims. developmental deformities in the African frog Streamwatch: Xenopus laevis. Although the concentrations In Australia: www.streamwatch.org.au/main.jsp used were much higher than would be expected Regulatory and governmental sites: Cooperative Research Centre for Water Quality if the product was used according to directions, and Treatment: National Industrial Chemicals Notification and they still indicate cause for concern, especially www.waterquality.crc.org.au/ Assessment Scheme (NICNAS): in cases where the amounts used do not comply www.nicnas.gov.au/australia/NRA.html with the label directions. International sites: The National River Contaminants Program: Swedish EPA: So, products previously considered safe for www.rivers.gov.au www.internat.naturvardsverket.se/index.php3 frogs may not be so safe after all. Here are some other questions for you. What do we The Environmental Protection Agency: WWF Canada. Reducing your risk to pesticides: really know about the products used in the - NSW: www.epa.nsw.gov.au www.wwf.ca/satellite/reduce-risk/index.html home and garden? Many chemicals are labelled - NSW EPA | What are pesticides? Agency for Toxic Substances as “Readily Biodegradable”, but what do they www.epa.nsw.gov.au/envirom/pestwhtr.htm and Disease Registry: degrade to? Its not specified on the label. In www.atsdr.cdc.gov/atsdrhome.html fact, many ingredients are not listed on the label - SA: www.environment.sa.gov.au/epa/epa/ (Agency of the U.S. Department of Health at all, or simply generalised to: “sudsing agent”, Australian Pesticides & Veterinary and Human Services - it provides information “thickener”, “cleaning agent” and the like. Of Medicines Authority: on substances and priority lists of the most course, many products really are safe to use - www.apvma.gov.au hazardous ones and includes some very thorough reviews) but which ones? for how long? and safe for Department of Environment & Heritage: what animals? I mention all this in order to raise US EPA: questions in your mind about the products we Department of Environment and Heritage: www.epa.gov www.deh.gov.au use everyday. US EPA Office of Pesticide Programs: Inland Waters: www.epa.gov/pesticides/ (Highly recommended site). www.deh.gov.au/water/ US EPA Office of Pollution Prevention & Toxics: National Pollutant Inventory: www.epa.gov/opptintr/index.html www.npi.gov.au (this site has thorough reviews, California Department of Pesticide Regulation: but only includes a limited number of pollutants) www.cdpr.ca.gov

11 TAKING ACTION

United States Department of Agriculture: So what can you do? Consider where you are using the product. www.usda.gov/ Since easy answers are not at our fingertips, When it rains will it just wash off into the Pesticide databases: we need to employ some basic common sense. nearest pond, catchment or drain? What www.cipm.ncsu.edu/index.html Sometimes a non-chemical method of cleaning happens then? Can you prevent this runoff? The EXtension TOXicology NETwork EXTOXNET: or pest control is as effective as a chemical It’s often easier to exclude pests than ace.orst.edu/info/extoxnet/ alternative. Sometimes we can minimize the to control them. You can often prevent (Highly recommended site for specific pesticide chemicals we perhaps need to use, and any cockroaches and household insect pests information - easy to use) reduction is a step in the right direction for by removing food scraps and storing food our frogs. in sealed containers. Block off indoor pest Environmental, lifestyle hiding places. Use sticky traps. Remove and personal sites: My common-sense ideas would be these: standing water, such as under indoor plants, Burke’s Backyard, chemical disposal: First, don’t use chemicals gratuitously. and fix leaky pipes, because even pests www.burkesbackyard.com.au/2002/archives/ Be reasonable. Ask yourself if your lawn need water. 2002/conservation_&_the_environment/ has to be completely free of weeds, can chemical_disposal Most importantly, always read the label and you choose hardier plants, do you need to use according to instructions. Its important www.rfu.org/AboutPulp.htm bleach the bathroom every week, and so on. to not only read the label before buying (about the pulp and paper industry) If its not really necessary, then don’t use it. the product, but also to read the label every Environmental Media Services: Use compost in preference to a commercial time you want to mix or use the product, www.ems.org/household_cleaners/information.html fertiliser. If you don’t want to compost, and before storing or disposing of it. (some great info on alternative cleaners and links at least try more natural alternatives such Many contamination events are because to other sites) as manure, seaweed, and fish emulsion formulations have been used incorrectly: Reach For Unbleached! - Consumer education fertilisers. The timing and placement of Sometimes people simply don’t read the about paper and pulp mill monitoring fertilisers can minimise off-site losses label; or they have used the product for www.rfu.org/index.htm through runoff. Placement within the soil years, without checking to see if WWF: is preferable to surface application. the formulation has changed; or people www.wwf.org.au use products just before it rains, so the Take advantage of web-based sites and product washes straight off into the nearest material to check the products you think waterway. Formulations for high volume you will be using often. You may have a rates might be used with low volume choice between a few different products – equipment, concentrating it; or people these sites might help you decide which may add just a little more to make sure. would be the least damaging. I’m sure we have all done this in cooking! If you need it for a specific purpose or pest, When it comes to being frog-friendly, try to use products with very narrow modes though, its not worth the risk. of action rather than broad spectrum ones If the chemical treatment didn’t work, do that have across-the-board effects. For not assume that using more pesticide than example, a number of insecticides are insect the label recommends will do a better job. growth regulators, and interfere with specific It won’t. You will need to find an alternative. moulting processes. One example is precor, a flea control liquid. These narrow mode products are less likely to have an impact on vertebrates.

12 What can you do with leftover hazardous DON’T pour leftover products or Oven cleaner: Try a baking soda, salt and household products or pesticides? pesticides: water paste. DO: Down storm drains or into creeks, Mildew: Scrub with a mix of borax because storm drains often send water and water on a scouring sponge. Try to use up all of the product. directly to our creeks or the ocean without Full strength vinegar is more powerful, If you simply can’t use it anymore, treatment. Toxins can poison fish, plants and but don’t forget to rinse. Again, avoid then give useable, leftover products to tadpoles, and can even end up in drinking chlorine based mold killers. friends or neighbours. water supplies. Toilet: Clean often with baking soda. Take unwanted products and potentially Down your sink or toilet, because many Let a cup of borax stand in the bowl dangerous waste to a household hazardous chemicals may pass through the treatment overnight for a more serious clean. waste disposal program (see below). plant untreated, and poison waterways. Furniture polish: Use almond, walnut, olive, They may even interfere with the operation Sydney Water runs a tremendous household or linseed oil. of wastewater treatment systems. chemical collection program, where you can Wash your car on the lawn if possible, drop off most types of chemicals, paints and On the ground, because they may so that the soap doesn’t run into the like. Phone 1800 814 719. seep into groundwater or be washed the storm water drains. down storm drains. - National Chemical Collection initiative Fleas: Obviously the first step is to vacuum within Australia Into your garbage bin, because they could regularly and washing pet bedding often. Phone 1800 008 182 seep into our groundwater from the landfill. Empty the vacuum cleaner bag every time www.chemclear.com.au However, water-based paints could be left to and seal in a bag in the garbage. Steam dry out and then placed in the garbage bin. - EcoRecycle Victoria (03) 9639 3322 cleaning carpet may also kill adult and or Infoline: 1800 353233 (within Victoria). Lastly, don’t burn them, because they often juvenile fleas. Try using an insect growth www.ecorecycle.vic.gov.au also release toxic fumes when they burn. regulator to prevent larvae from maturing. Pyrethrins are considered the least harmful - DrumMuster (national program for the Some alternative suggestions of the adult flea pesticides, but be careful collection and recycling of empty, cleaned, (however, I have not personally tested that the pyrethrin isn’t mixed with other non-returnable farm chemical containers). all of them): more toxic ingredients. Wash pets with Phone: (02) 62306712. Degreasers: Use citrus-based or a citrus oil shampoo and use a flea comb. www.drummuster.com.au water-based detergents. Avoid products Sometimes herbal flea collars with with methylene chloride. ingredients such as eucalyptus, citronella and cedarwood can work well. Detergents: Avoid products with phosphates. Try laundry soaps. AVOID chlorine bleaches. Mosquitoes: Screens on windows and If you need bleach, use a hydrogen-peroxide doors are the biggest help. Remove standing based one. water near the house. Frogs and spiders are great insect predators so encourage them Surface cleaners: Try lemon juice and to hang around! If you must use a repellent, vinegar to cut grease. Borax can be try citronella ones. And avoid wearing used to soften water in order to prevent strong-smelling products (which seem soapy deposits. Try to use vegetable to attract mosquitoes). oil based soaps. To be frog-friendly, we all need to Drain openers: Using a sink strainer consider our choices and their potential eliminates most problems. Pour boiling for harm. water down drains once a week to eliminate grease. If a drain is partially clogged, try putting in some baking soda with 1/2 a cup of vinegar, and seal the drain. This produces carbon dioxide bubbles which may dislodge the obstruction. Uncover and follow with boiling water.