The relationship of Irgarol and its major metabolite to resident phytoplankton communities in a Maryland marina, river and reference area

The objectives of this study were to: (1) measure water column concentrations of Irgarol 1051 and its major metabolite GS26575 annually (2004-2006) during mid-June and mid-August at 14 sites in a study area comprised of three sub-regions chosen to reflect a gradient in Irgarol exposure (Port Annapolis marina, Severn River and Severn River reference area); (2) use a probabilistic approach to determine ecological risk of Irgarol and its major metabolite in the study area by comparing the distribution of exposure data with toxicity-effects endpoints; and (3) measure both functional and structural resident phytoplankton parameters concurrently with Irgarol and metabolite concentrations to assess relationships and determine ecological risk at six selected sites in the three study areas described above. The three-year summer mean Irgarol concentrations by site clearly showed a gradient in concentrations with greater values in Back Creek (400-500 ng/L range), lower values in the Severn River sites near the confluence with Back Creek (generally values less than 100 ng/L) and still lower values (<10 ng/L) at the Severn River reference sites at the confluence with Chesapeake Bay. A similar spatial trend, but with much lower concentrations, was also reported for GS26575. The probability of exceeding the Irgarol plant 10th centile of 193 ng/L and the microcosm NOEC (323 ng/L) suggested high ecological risk from Irgarol exposure at Port Annapolis marina sites but much lower risk at the other sites. There were no statistically significant differences among the three site types (marina, river and reference) with all years combined or among years within a site type for the following functional and structural phytoplankton endpoints: algal biomass, gross photosynthesis, biomass normalized photosynthesis, chlorophyll a, chlorophyll a normalized photosynthesis and taxa richness. Therefore, based on the above results, Irgarol adverse effects predicted from the plant 10th centile and the microcosm NOEC in the high Irgarol exposure area (Back Creek/Port Annapolis marina) were not confirmed with the actual field data for the receptor species (phytoplankton). These results also highlight the importance of unconfined field studies with a chemical gradient in providing valuable information regarding the responses of resident phytoplankton to herbicides.     

Occurrence and transport of Irgarol 1051 and its major metabolite in coastal waters from South Florida

Irgarol 1051, a boosting antifouling agent often used to supplement copper based paints was found in surface waters from South Florida at stations collected from the Miami River, Biscayne Bay and selected areas of the Florida Keys. Concentrations of the herbicide ranged from below the method detection limit (1 ng/L) to as high as 182 ng/L in a canal system in Key Largo. The herbicide was present at 93% of the stations and often found in conjunction with its descyclopropyl metabolite (M1) previously reported to be the major degradation product of Irgarol under natural environmental conditions. The 90th percentile concentration calculated for all South Florida samples was 57.6 ng/L. Based on available data on the toxicity of Irgarol to algae and coral, only two stations (approximately 3%) ranked above the LC50 of 136 ng/L reported for the marine algae Naviculla pelliculosa and above the 100 ng/L level reported to reversibly inhibit photosynthesis of intact corals. However, a basic dissipation model for Irgarol using the Key Largo Harbor station as a point source indicated that concentrations of the herbicide decreased rapidly and concentrations below the MDL are observed within 2000 m of the source. No major coral based benthic habitats are documented for all the stations surveyed at distances that Irgarol may pose a substantial risk. However, other types of submerged vegetation like seagrasses are common around the marinas and the effects of Irgarol to such endpoints should be investigated further.     

Inhibition of coral photosynthesis by the antifouling herbicide Irgarol 1051

International regulation of organotin compounds for use in antifouling paints has led to the development and increased use of replacement compounds, notably the s-triazine herbicide Irgarol 1051. Little is known about the distribution of Irgarol 1051 in tropical waters. Nor has the potential impact of this triazine upon photosynthesis of endosymbiotic microalgae (zooxanthellae) in corals been assessed. In this study Irgarol 1051 was detected in marinas, harbours and coastal waters of the Florida Keys, Bermuda and St. Croix, with concentrations ranging between 3 and 294 ng 1(-1). 14C incubation experiments with isolated zooxanthellae from the common inshore coral Madracis mirabilis showed no incorporation of H14CO3- from the sea water medium after 4-8 h exposure to Irgarol 1051 concentrations as low as 63 ng 1(-1). Reduction in net photosynthesis of intact corals was found at concentrations of l00 ng 1(-1) with little or no photosynthesis at concentrations exceeding 1000 ng 1(-1) after 2-8 h exposure at all irradiances. The data suggest Irgarol 1051 to be both prevalent in tropical marine ecosystems and a potent inhibitor of coral photosynthesis at environmentally relevant concentrations.     

Assessment of TBT and organic booster biocide contamination in seawater from coastal areas of South Korea

Seawater samples from major enclosed bays, fishing ports, and harbors of Korea were analyzed to determine levels of tributyltin (TBT) and booster biocides, which are antifouling agents used as alternatives to TBT. TBT levels were in the range of not detected (nd) to 23.9 ng Sn/L. Diuron and Irgarol 1051, at concentration ranges of 35–1360 ng/L and nd to 14 ng/L, respectively, were the most common alternative biocides present in seawater, with the highest concentrations detected in fishing ports. Hot spots were identified where TBT levels exceeded environmental quality targets even 6 years after a total ban on its use in Korea. Diuron exceeded the UK environmental quality standard (EQS) value in 73% of the fishing port samples, 64% of the major bays, and 42% of the harbors. Irgarol 1051 levels were marginally below the Dutch and UK EQS values at all sites.     

Occurrence of Irgarol 1051 and its major metabolite in Maryland waters of Chesapeake Bay

Irgarol and its major metabolite (GS26575) were measured in Maryland waters of Chesapeake Bay: (1) in and near 10 marinas, a mainstem Bay site and two Severn River locations during a general survey in July and December of 2002; (2) at various sites in the Port Annapolis Marina and the Severn River area during March of 2002 before the boating season began; and (3) during July (peak boating season) in the same Port Annapolis Marina and Severn River sites area during both an ebb and flood tide. Irgarol concentrations ranged from 1.82 ng/l at the mid-Bay site to 585 ng/l in Port Annapolis marina during the July and December general survey. An Irgarol 90th centile of 239 ng/l was reported for the 10 marina sites, two Severn River sites and one mainstem site sampled during the general survey conducted in July and December. Temporal analysis of all pooled data showed that 90th centiles were over seven times higher in July when compared to December. A comparison of Irgarol concentrations at 12 sites in the Port Annapolis marina and Severn River area during both an ebb and flood tide in July showed no consistent trend with tidal cycle by site although significant reductions in concentrations were reported with distance from the three Port Annapolis marina sites. Ecological risk from Irgarol exposure was judged to be low for most Chesapeake Bay sites sampled. Possible exceptions were Port Annapolis marina, Severn River sites in close proximity to this marina and Chesapeake Harbor marina where Irgarol concentrations exceeded a conservative effects threshold during the peak boating season in July. Ecological risk from GS26575 exposure was low for all sites.     

Probabilistic risk assessment of common booster biocides in surface waters of the harbours of Gran Canaria (Spain)

The presence of booster biocides in the aquatic environment has been associated with a risk to non-target species due to their proven toxicity. The aim of the present study was to determine the spatial and temporal distribution of common booster biocides in different harbours of the island of Gran Canaria (Spain) and evaluate, by means of a probabilistic risk assessment (PRA), the ecological risk posed by these compounds. With these objectives, a monitoring campaign was conducted between January 2008 and May 2009, collecting a total of 182 seawater samples. Four common booster biocides (TCMTB, diuron, Irgarol 1051 and dichlofluanid) were monitored. Diuron levels ranged between 2.3 and 203 ng/L and Irgarol 1051 between 2.4 and 146.5 ng/L. The ecological risk associated with these levels was always low, however, with probabilities of exceeding the 10th percentile of autotroph toxicity below 3.5%.     

Extent and magnitude of copper contamination in marinas of the San Diego region, California, USA

Marinas are areas of special water quality concern because of the potential for pollutant accumulation within their protected waters. Perhaps the largest contaminant source to marinas is antifouling paints that leach copper to prevent the growth of encrusting organisms on vessel bottoms. Very little monitoring of marinas is typically conducted despite the potential environmental risk, particularly in the San Diego region of California, USA where as many as 17,000 recreational vessels are berthed. The objective of this study was twofold: (1) determine the extent and magnitude of dissolved copper concentrations in marinas throughout the San Diego region, and (2) determine if elevated copper concentrations in marinas of the San Diego region are resulting in adverse biological impacts. A probabilistic study design was used to sample water column copper concentrations and toxicity (using Mytilus galloprovincialis) at 30 stations. Results indicated that exceedence of state water quality objectives was widespread (86% of marina area), but that toxicity was much less prevalent (21% of marina area). Toxicity identification evaluations (TIEs) conducted at the most toxic sites indicated that toxicity was largely due to trace metals, most likely copper. Toxicity was reduced using TIE treatments that chelated trace metals such as cation exchange column, ethylenediaminetetraacetic acid (EDTA), and sodium thiosulfate (STS). Moreover, increasing dissolved copper concentrations correlated with increasing toxicity and these copper concentrations were high enough to account for virtually all of the observed toxicity.     

Organotin and Irgarol-1051 contamination in Singapore coastal waters

The seas surrounding Singapore are principally utilized by the shipping industry but are now also increasingly used for a variety of other purposes, including desalination for supplies of drinking water and intensive aquaculture of food fish. While stringent environmental pollution standards are in place for industrial effluents, there is currently no legislative control over pollution from anti-fouling paints in Singapore. In this study, the concentrations of toxic antifouling agents tributyltin (TBT), triphenyltin (TPhT) and Irgarol-1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) were determined from seawater obtained from 26 locations along and off the coast of Singapore in October and November 2000. These compounds were isolated by liquid-liquid extraction derivatized under controlled microwave heating and quantified by gas chromatography-mass spectrometry. TBT concentrations in seawater ranged between 0.43 and 3.20 microg 1(-1) with a mean value of 1.40 +/- 0.60 micro 1(-1). The mean values of DBT and MBT were 1.07 +/- 0.80 microg 11(-1) and 0.34 +/- 0.50 microg 1(-1) respectively, while TPhT concentrations of up to 0.40 microg 1(-1) were found. Monophenyltin and diphenyltin were not detected in all samples analysed. Irgarol-1051 was found to be present at concentrations of between 3.02 microg 1(-1) and 4.20 microg 1(-1) in seawater with a mean value of 2.00 +/- 1.20 microg 1(-1).     

Occurrence of IRGAROL 1051 in coastal waters from Biscayne Bay,Florida, USA

Surface water samples from marinas, commercial ports and open bay areas collected from Biscayne Bay and the Miami River, Florida, USA, were analyzed for the occurrence of IRGAROL 1051 by GC/MS. The anifouling boosting herbicide was found in 80% (46/57) of the samples collected between March 1999 and September 2000. Concentrations within the bay range between non-detected (<1 ppt) and 61 ppt (ng/L) and were generally low compared with levels reported in European or Japanese waters. Aside from the elevated concentrations observed along the Miami River South Fork (61 ppt), the highest concentrations observed in the bay corresponded to marinas with high density of pleasure craft and restricted water circulation. In contrast, occurrence of IRGAROL 1051 along the commercial port or the cruise line terminal was generally lower (<1-2.2 ppt). Concentrations around Coconut Grove Marina were consistently higher (5-12 ppt) than the rest of the bay waters during the whole period of time surveyed.     

Toxicities of antifouling biocide Irgarol 1051 and its major degraded product to marine primary producers

Irgarol 1051 (2-methythiol-4-tert-butylamino-6-cyclopropylamino-s-triazine) is an algaecide commonly used in antifouling paints. It undergoes photodegradation which yields M1 (2-methylthio-4-tert-butylamino-6-amino-s-triazine) as its major and most stable degradant. Elevated levels of both Irgarol and M1 have been detected in coastal waters worldwide; however, ecotoxicity effects of M1 to various marine autotrophs such as cyanobacteria are still largely unknown. This study firstly examined and compared the 96 h toxicities of Irgarol and M1 to the cyanobacterium Chroococcus minor and two marine diatom species, Skeletonema costatum and Thalassiosira pseudonana. Our results suggested that Irgarol was consistently more toxic to all of the three species than M1 (96 h EC50 values: C. minor, 7.71 microug L(-1) Irgarol vs. > 200 microg L(-1) M1; S. costatum, 0.29 microg L(-1) Irgarol vs. 11.32 microg L(-1)M1; and T. pseudonana, 0.41 microg L(-1) Irgarol vs. 16.50 microg L(-1)M1). Secondly, we conducted a meta-analysis of currently available data on toxicities of Irgarol and M1 to both freshwater and marine primary producers based on species sensitivity distributions (SSDs). Interestingly, freshwater autotrophs are more sensitive to Irgarol than their marine counterparts. For marine autotrophs, microalgae are generally more sensitive to Irgarol than macroalgae and cyanobacteria. With very limited available data on M1 (i.e. five species), M1 might be less toxic than Irgarol; nonetheless this finding warrants further confirmation with additional data on other autotrophic species.     

Toxicities of antifouling biocide Irgarol 1051 and its major degraded product to marine primary producers

Irgarol 1051 (2-methythiol-4-tert-butylamino-6-cyclopropylamino-s-triazine) is an algaecide commonly used in antifouling paints. It undergoes photodegradation which yields M1 (2-methylthio-4-tert-butylamino-6-amino-s-triazine) as its major and most stable degradant. Elevated levels of both Irgarol and M1 have been detected in coastal waters worldwide; however, ecotoxicity effects of M1 to various marine autotrophs such as cyanobacteria are still largely unknown. This study firstly examined and compared the 96 h toxicities of Irgarol and M1 to the cyanobacterium Chroococcus minor and two marine diatom species, Skeletonema costatum and Thalassiosira pseudonana. Our results suggested that Irgarol was consistently more toxic to all of the three species than M1 (96 h EC50 values: C. minor, 7.71 μg L⁻¹ Irgarol vs. >200 μg L⁻¹ M1; S. costatum, 0.29 μg L⁻¹ Irgarol vs. 11.32 μg L⁻¹ M1; and T. pseudonana, 0.41 μg L⁻¹ Irgarol vs. 16.50 μg L⁻¹ M1). Secondly, we conducted a meta-analysis of currently available data on toxicities of Irgarol and M1 to both freshwater and marine primary producers based on species sensitivity distributions (SSDs). Interestingly, freshwater autotrophs are more sensitive to Irgarol than their marine counterparts. For marine autotrophs, microalgae are generally more sensitive to Irgarol than macroalgae and cyanobacteria. With very limited available data on M1 (i.e. five species), M1 might be less toxic than Irgarol; nonetheless this finding warrants further confirmation with additional data on other autotrophic species.     

Determination of Irgarol-1051 and its related s-triazine species in coastal sediments and mussel tissues by HPLC-ESI-MS/MS

A mild, low-temperature analytical approach based on sonication assisted extraction coupled with HPLC electrospray ionization triple quadrupole tandem mass spectrometry has been developed for the simultaneous qualitative and quantitative determination of the four Irgarol-related s-triazine species, namely Irgarol-1051, M1, M2 and M3, in coastal sediments and Green-lipped mussel samples. Mild extraction conditions were necessary for the preservation of the thermally unstable M2. The Multiple Reaction Monitoring (MRM) mode of detection by ESI-MS/MS enabled reliable qualitative identification and sensitive quantitative determination of those s-triazines. This determination method was applied to evaluate the degree of Irgarol-1051 contamination in the sediments and biota of the coastal environment of Hong Kong - one of the busiest maritime ports in the world. All the four s-triazine species were observed in all of the samples. This is the first time that the newly identified M2 and M3 are detected in coastal sediments and biota tissues.     

The impact of legislation on the usage and environmental concentrations of Irgarol 1051 in UK coastal waters

In 2001, legislative measures were introduced in the UK to restrict usage of antifouling agents in small (<25 m) vessel paints to dichlofluanid, zinc pyrithione and zineb. This removed the previously popular booster biocides diuron and Irgarol 1051 from the market. To investigate the impact of this legislation, water samples were taken from locations where previous biocide levels were well documented. Results from analyses demonstrate a clear reduction in water concentrations of Irgarol 1051 (between 10% and 55% of that found during pre-restriction studies), indicating that legislation appears to have been effective. Although other booster biocides were screened for (chlorothalonil, dichlofluanid and Sea-Nine 211), they were below the limits of detection (<1 ng/l) in all samples. A survey of chandlers and discussions with legislative authorities supports these results and concurs the removal of Irgarol 1051 based paints from the market using simple regulations at a manufacturer level with little regulation at a retailer level.     

Trace metals in antifouling paint particles and their heterogeneous contamination of coastal sediments

Antifouling paint residues collected from the hard-standings of a marine leisure boat facility have been chemically characterised. Scanning electron microscopy revealed distinct layers, many containing oxidic particles of Cu and Zn. Quantitative analysis indicated concentrations of Cu and Zn averaging about 300 and 100 mg g⁻¹, respectively, and small proportions of these metals (<2%) in organometallic form as pyrithione compounds. Other trace metals present included Ag, Cd, Cr, Ni, Pb and Sn, with maximum concentrations of about 330, 75, 1200, 780, 1800 and 25,000 μg g⁻¹, respectively. Estuarine sediment collected near a boatyard contained concentrations of Cu and Zn an order of magnitude greater than respective concentrations in “background” sediment, and mass balance calculations suggested that the former sample was contaminated by about 1% by weight of paint particles. Clearly, antifouling residues represent a highly significant, heterogeneous source of metallic contamination in the marine environment where boating activities occur.     

Ecological risk assessment of eutrophication in Songhua Lake, China

The Songhua Lake in the Northeast China is chosen as a study case in this paper. Monitoring of samples and analysis 18 indexes related to the eutrophication in the Songhua Lake had been conducted in 2002–2004. Ecological risk assessment methods are employed here. The study results showed that total phosphorus and total nitrogen were main risk factors to impact on the eutrophication of the Songhua Lake, and influence of the phosphorus on the lake eutrophication was larger than that of nitrogen. Algal growth potential test was also conducted to validate the results. High phosphorus and high nitrogen concentrations were mostly distributed in Huifahekou and Jiaohe sites of the Songhua Lake. Threshold values of total phosphorus, total nitrogen and Chl-a concentrations from dose-effective examination were 0.065 mg/L, 0.843 mg/L, and 11.90 μg/L, respectively. The probability of the eutrophication appeared in the Songhua Lake was 0.69, of them, risk-free type area was 19.21% of total lake area, slight risk type area was 30.10%, middle risk type area was 16.50%, heavy risk type area was 25.8%, hyper risk type area was 8.39%. In order to control the eutrophication in the Songhua Lake, maximum permission discharges of total phosphorus and total nitrogen to the lake would be 2,123.78, 7,018.82 t/a, respectively.     

Impact of multi-annual drought on streamflow and habitat in coastal California salmonid streams

The 2012–2015 drought in north-central coastal California ranks among the three most prolonged periods of below-median annual rainfall in the past 65 years. In three critical coho salmon streams, summer baseflow was less each additional dry year; streams with summer flow early in the drought had no flow for more than two months in latter years. By the third dry year, summer discharge was 1–5% of recent wet-type years, and 10–20% of the first dry year. Multiannual drought also caused increased dry channel conditions: the percentage of flowing channel reduced from 28 to 55% from the first to the third dry years among three study streams. In the first year following drought, dry-season streamflow resembled early to-mid-drought conditions, while in the second, it approached pre-drought discharge. This multiannual drought foreshadows how multi-annual drought predicted under future climate scenarios may affect critical salmonid streams later this century.     

Comparability of bioaccumulation within the sanddab guild in coastal Southern California

Most assessments of fish contamination in Southern California use ecologically different species from different sites. Use of ecologically similar species (a guild) might provide better assessments of fish contamination across different sites and depths. In July-August 1997, we collected samples of four sanddab guild species at 22 sites where species pairs co-occurred and determined total DDT concentrations in homogenized whole fish composites. Log-transformed DDT concentrations were highly correlated among all species pairs within this guild. All relationships were linear over the range observed, with slopes not statistically different from unity. The variability in response among species was about four times the variability encountered among replicates within species, but 15 times smaller than the variability among sites. Together, these results suggest that the sanddab guild, widespread on soft bottoms of the Southern California coastal shelf, can be used as a "superspecies" in bathymetrically diverse regional assessments of fish tissue contamination.     

Distribution and ecological risk assessment of some heavy metals in coastal surface sediments along the Red Sea,Egypt

The ecological risk assessment for Al,Zn,Cu,Ni,V,Pb,Cd,and Hg in surface sediment collected from the Egyptian Red Sea coast was evaluated using the Geo-accumulation Index(I_(geo)).Sediment Enrichment Factor(SEF) and Potential Ecological Risk Index(PERI) methods.The predominant heavy metal,aluminum,showed high concentrations along both of Aqaba Gulf(4378.8 ± 2554.1 μg/g) and southern part of the Red Sea(2972.8 + 1527.5 μg/g).while it recorded the lowest concentration in Suez Gulf(829.7 ± 398.2 μg/g).The determined heavy metal concentrations had the order of Al Zn -Ni V Pb Cu Cd Hg.The statistical analyses showed some correlations among the heavy metals contents.Several international sediment quality guidelines were used to estimate the quality of the collected sediments.Interestingly,the recorded average heavy metals concentrations were lower than those of the permissible contents for sediment quality guidelines.The Geo-accumulation index calculations(I_(geo)) proved that the investigated region could be classified as an unpolluted area.Sediment Enrichment Factor(K_(SEF)) study showed high values in Suez Gulf region.The single pollution index analysis of heavy metals in the sediments(C~i_f) indicated that Al,Zn,V,and Pb were of natural origin,while Ni,Cd and Hg were seriously affected by human activities.Interestingly,amongst,all the determined heavy metals,Cd and Hg gave moderate ecological risk indicators.     

太湖流域苏州城区不同用地类型降雨径流中重金属的生态风险评价

随着城市化进程的不断加快,不同用地类型上产生的降雨径流中重金属含量高且差异较大,而目前仍缺乏对降雨径流所携带的重金属风险评价的研究.以苏州城区为研究对象,选取商业区、居住区、历史文化保护区和文教区,监测降雨径流中铜（Cu）、锌（Zn）和铅（Pb）3种常见重金属浓度,通过物种敏感性分布（SSD）曲线获取预测无效应浓度（PNEC）,基于重金属的生态有效性,应用风险商（RQ）法对重金属的生态风险进行评价.结果表明：以6场有效降雨事件的事件平均浓度（EMC）统计结果的平均值为分析依据,对照《地表水环境质量标准》（GB 3838—2002）,苏州城区径流中的Zn、Cu浓度满足Ⅱ类水质标准,Pb浓度则劣于Ⅴ类水质标准;主要受地面交通活动和屋面材料的影响;在不同用地类型内Cu、Pb和Zn浓度的分布存在一定差异,商业区受重金属污染程度最为严重,其余3种用地类型均不同程度受到不同重金属的污染,对应的3种重金属的生态风险在不同用地类型内也显示相同规律;不同的重金属产生不同的环境行为,导致对水生生物的毒性差异较大,降雨径流中的重金属浓度在水环境中产生的有效生态风险程度为Pb > Cu > Zn.研究认为Cu、Zn和Pb对淡水生物的生态风险均达到高风险程度,而我国目前的《地表水环境质量标准》未充分考虑生态影响,低估了部分重金属的生态风险.     

Natural and anthropogenic controls on sediment rating curves in northern California coastal watersheds

The watersheds along the north coast of California span a wide range of geologic settings, tectonic uplift rates, and historic timber harvest activity. Known trends in how each of these factors influence erosion rates provides an opportunity to examine their relative importance. We analyzed 71 watersheds within nine larger river basins, investigated the factors influencing suspended sediment rating curves (SRCs), investigated how SRCs varied among our study watersheds, and used Random Forest modeling (RFM) to determine which environmental characteristics and land management metrics influence SRC shapes, vertical offsets, and slopes. While SRCs typically take the form of a power function, they also can exhibit threshold or peak relationships. First, we found both power and threshold relationships for the SRCs within our study watersheds. Second, the SRC offsets and slopes systematically varied with regional tectonic uplift. Third, SRC offsets increased in several watersheds following intensive timber harvest events and SRC slopes decreased due to a greater relative increase in suspended sediment concentration at lower flows than higher flows. Our RFM correctly classified 96% of the SRC shapes using two near-channel metrics; near-channel precipitation-sensitive deep-seated landslide susceptibility and near-channel soil erodibility. Our RFM models also showed that timber harvest activity and near-channel local relief can explain 40% of the variability in SRC offsets, whereas tectonic uplift rates, millennial-scale erosion rates, and precipitation patterns explain 40% of the variability in SRC slopes.