**5. List of abbreviations**

204 Chromatography – The Most Versatile Method of Chemical Analysis

their metabolites in environmental samples [47, 55].

environments.

the same run.

**4. Conclusion**

allows the molecule to "wrap" itself around that cation [64]. Thus, sodium acetate [60, 74], ammonium acetate [89, 142] or different acids [53] are commonly added to the samples or to the mobile phase to increase the MS response of NPEOs and AEOs and to stabilize the generation of [M+Na]+, [M+NH4]+ or [M+H]+ ions, among others. Additionally, this ability to form different adducts can be used to obtain multiple confirmation points in full-scan mode [40]. Another advantage of MS compared to other detectors is that several types of surfactants can be analyzed within a single run (e.g., NPEOs and AEOs can be separated, using an adequate gradient, and later analyzed under PI [53, 64]). Most recent methodologies allow simultaneous determination of anionic and non-ionic surfactants and

Today, mass spectrometry is often combined with ultra-performance liquid chromatography (UPLC), which uses sub-2-µm column particles that provide enhanced separation, faster analysis, and improved sensitivity over HPLC, boosting laboratory efficiency by saving time and decreasing solvent consumption. Most researchers have started to benefit from this combination, although there are still a few examples on its use for analysis of surfactants. So far, UPLC-Q-ToF-MS has been used for structural elucidation of SPC isomers [139] and for environmental screening of several anionic and non-ionic surfactants in wastewater [138]. UPLC-MS-MS [44] has allowed achieving fast analysis (less than 10 min per sample) of NPEO metabolites and AEOs at trace levels in aquatic

The assessment of the behavior and final fate of synthetic surfactants in the environment is a crucial matter due to the huge volumes of these chemicals that are discharged into aquatic and terrestrial ecosystems. A significant number of analytical protocols have been developed over the last decades aimed to the individual or simultaneous extraction, isolation and determination of different types of surfactants in environmental samples. Nowadays, the most widely used sample preparation protocols are based on SPE, directly derived from column chromatography. However, the trend is to research on new techniques, such as SPME or SBSE, aimed to reduce, or even eliminate, solvent consumption, as well as saving money by using reusable fibers and bars rather than disposable cartridges. Regarding the separation, identification and quantification of surfactants, HPLC-MS and, to a lesser extent due to the non volatility of most analytes, GC-MS, are the main tools currently employed as they allow for determination of every single homologue, ethoxymer and/or isomer from surfactant mixtures in different environmental matrices (solids, water and biota). Most recently, different classes of time-of-flight and triple quadrupole mass spectrometers have started to be combined with UPLC, which provides enhanced separation, faster analysis, higher confidence, and lower detection limits than more conventional HPLC-MS or HPLC-MS-MS approaches, as well as improves identification of unknown surfactant metabolites and other non target compounds within AA, Acetic acid; ASE, Accelerated solvent extraction; ACN, Acetonitrile; AEOs, Alcohol polyethoxylates; AES, Alkyl ethoxysulfates; AS, Alkyl sulfates; ATACs, Alkyltrimethylammonium chlorides; AP, Alkylphenol; APEOs, Alkylphenol polyethoxylates; APEC, Alkylphenol polyethoxycarboxylate; AMAC, Ammonium acetate; APCI, Atmospheric pressure ionization; BACs, Benzalkonium chlorides; BSTFA, N,Obis(trimethylsilyl)trifluoro acetamide; CWAX/TR, Carbowax/template resin; CI, Chemical ionization; DTDMAC, Dehydrogenated tallow dimethyl ammonium chloride; DADMAC, Dialkyldimethylammonium chlorides; DCM, Dichloromethane; DLLME, Dispersive liquidliquid microextraction; EI, Electron impact ionization; ESI, Electrospray ionization; EO, Ethylene oxide; CESIO, European Committee of Organic Surfactants and their Intermediates; FID, Flame-ionization detectors; FIA, Flow-injection analysis; FL, Fluorescence detectors; FA, Formic acid; GC, Gas chromatography; GBC, Graphitized black carbon; HPLC, High-performance liquid chromatography; HLB, Hydrophilic-lipophilic balance; LOD, Limit of detection; LOQ, Limit of quantification; LAS, Linear alkylbenzene sulfonates; LC, Liquid chromatography; LLE, Liquid-liquid extraction; MS, Mass spectrometry; MSPD, Matrix solid-phase dispersion; MeOH, Methanol; MLD, Method limit detection; MAE, Microwave-assisted extraction; NC, Naphthyl chloride; NI, Negative ionization; NP, Nonylphenol; NPEOs, Nonylphenol polyethoxylates; NPECs, Nonylphenol polyethoxycarboxylates; OP, Octylphenol; OPEOs, Octylphenol polyethoxylates; PA, Polyacrylate; PEGs, Polyethylenglycols; SDB, Polystyrene-divinylbezene; PDMS/DVB, Polydimethylsiloxane/divinylbenzene; PI, Positive ionization; PT, Potentiometric titrametration; PFE, Pressurized fluid extraction; PLE, Pressurized liquid extraction; Q-ToF, Quadrupole time-of-flight; QACs, Quaternary ammonium-based compounds; SIM, Selected ion monitoring; SDS, Sodium dodecyl sulphate; SLE, Solid-liquid extraction; SPE, Solid phase extraction; SPME, Solid phase microextraction; SBSE, Stir-bar sorptive extraction; SAX, Strong anionic-exchange; SCX, Strong cationic-exchange; SPCs, Sulfophenyl carboxylic acids; SFE, Supercritical fluid extraction; MS-MS, Tandem mass spectrometry; ToF, Time-offlight; UPLC, Ultra performance liquid chromatography; UV, Ultraviolet detectors; WWTPs, Wastewater treatment plants.


**14.2 Surgical treatments**

The goal of surgery is to excise all visible endometriotic lesions and associated adhesionsperitoneal lesions, ovarian cysts, deep rectovaginal endometriosis-and to restore normal anatomy.

Laparoscopy is the gold standard for diagnosis and the primary means of treatment at this time. Laparoscopy is used with different goals such as diagnosis, ablation, excision and lysis of adhesions.

 Excisional removal of ovarian endometriomas seems superior to drainage and ablation for both improved spontaneous pregnancy rates and improved pain symptoms. Laparoscopic treatment of endometriosis carries a long-term substantial relief of symptoms for a significant percentage of women. (114) Laser ablation does not appear to be more effective than conventional electrosurgical ablation of endometriosis.

Radical procedures such as oophorectomy or total hysterectomy are indicated only in severe situations and can be performed either laparoscopically or by laparotomy. Laparotomy should be reserved for patients with advanced-stage disease who cannot undergo a laparoscopic procedure and for those in whom fertility conservation is not necessary.

Endometriosis 21

relapse of ureter endometriosis.(123) The laparoscopic approach for ureteral endometriosis is very well tolerated and has a reasonable incidence of complications, as well as a low rate

Considering the difficulty of achieving a strictly scientific approach to low disease prevalence, the surgeon dealing with ureteral endometriosis must adapt surgery to achieve a balance between conservative purposes and the risk of recurrence on the one hand, and a radical approach and risk of morbidity on the other. Ureterolysis could be used as the initial surgical step for patients with ureteral endometriosis, and may be the only treatment if the extension of ureteral involvement is limited in length and there is no residual ureteral

For patients displaying extended severe ureteral involvement, stenosis, or moderate or severe hydronephrosis with a high risk of having intrinsic ureteral disease, ureterolysis is probably insufficient and ureteroneocystostomy likely represents a wiser surgical strategy

Long-term probability of pain recurrence after repeat conservative surgery for recurrent endometriosis varies between 20 and 40%. The association of presacral neurectomy to the treatment of endometriosis might be effective in reducing midline pain; however, no studies have evaluated this procedure among patients with recurrent disease. The medium-term outcome of hysterectomy for endometriosis-associated pain is quite satisfactory; nevertheless, probability of pain persistence after hysterectomy is 15% and risk of pain worsening 3–5%, with a six times higher risk of further surgery in patients with ovarian preservation as compared to ovarian removal. The conception rate among women undergoing repetitive surgery for recurrent endometriosis associated with infertility is 26%, whereas the overall crude pregnancy rate after a primary procedure is

Repeat conservative surgery for pelvic pain associated with recurrent endometriosis has the same limitations as primary surgery, with long-term cumulative recurrence rates ranging from 20 to 40%. Conversely, only one woman out of four will conceive after repeat conservative surgery for infertility, almost half the pregnancy rate after primary surgery and

The treatment of endometriosis-related infertility is dependent on the age of the woman, the duration of infertility, the stage of endometriosis, the involvement of ovaries, tubes, or both in the endometriosis process, previous therapy, associated pain symptoms, and the priorities of the patient, taking into account her attitude toward the disease, the cost of

The success of surgery in relieving infertility is probably related to the severity of endometriosis. A recent retrospective multicenter analysis (125) reported cumulative pregnancy rates of 39%, 31%, 30%, and 25% in patients with endometriosis stages I , II, III,

Endometriosis-associated infertility can be successfully treated with intrauterine insemination, but only if it is done in combination with ovarian stimulation (126).

of recurrence.

damage or dilatation.

(124).

41%.

with no substantial advantages over IVF. (102)

treatment, her financial means, and the expected results.

and IV, respectively ,l2 months after surgical treatment.

Assisted Reproduction and Endometriosis:

In patients with severe endometriosis it has been recommended that surgical treatment be preceded by a 3-month course of medical treatment to reduce vascularization and nodular size (115).

Postoperative medical treatment is rarely indicated because it does not work based on randomized trials, because it prevents pregnancy, and the highest pregnancy rates occur during the first 6 to 12 months after conservative surgery (116, 117).

Presacral Neurectomy (PSN):

For some women, transection of presacral nerves lying within the interiliac triangle may provide relief of chronic pelvic pain. PSN is used in a limited manner and not recommended routinely for management of endometriosis related pain.

Laparoscopic presacral neurectomy can be offered to treat midline pelvic pain.(114, 118)

Deep Rectovaginal and Rectosigmoidal Endometriosis:

Surgical treatment of DIE (Deeply Infiltrating Endometriosis) requires a professional who is able to perform surgery in the gynaecological, urological, gastrointestinal and nervous structures of the pelvis, as the disease 'knows no boundaries'. There is no scientific validation either that a multispecialty team approach is superior for the treatment of bowel endometriosis, which could also make the multisurgeon model 'experimental' and therefore unethical. (119)

Preoperative laxatives, starch-free diet, and full bowel preparation are needed to allow perioperative bowel suturing, if needed. Ureter stents may be required before excision of peritoneal endometriosis surrounding the ureter. A multidisciplinary approach involving gynecologic and gastroenterologic surgeons and urologists is desirable.

Bladder endometriosis is rare .The common clinical manifestations of bladder endometriosis include menouria and urethral and pelvic pain syndrome occurring cyclically. Cystoscopy is the most useful diagnostic test with confirmation by histologic study. Treatment must be individualized according to the patient's age, desire for future pregnancies, the severity of the symptoms, the site affected, and whether other organs are involved. transurethral resection-endometrioma biopsy to confirm the diagnosis and hormone blockade with LH– RH analogues is the initial treatment most commonly used in recent years, despite an estimated recurrence of 25–35% .(120)

Analogues have been the medical treatment of choice because their introduction, and the estrogens, androgens, progestogens, and danazol used in previous years have fallen into disuse because they lead to more adverse effects. Analogues induce a postmenopause like anovulatory state, a hypogonadotropic hypogonadism with serum estrogen concentrations dropping to sterilization levels, which causes the endometrial tissue to regress. (121, 122)

Ureter endometriosis was related with reproductive tract endometriosis. It has insidious process resulting in difficulty for early diagnosis. It's important to treat pelvic deep infiltrating endometriosis and ovarian endometrioma to prevent ureter from further involvement. Post-operative treatment of pelvic endometriosis is the key point of preventing

In patients with severe endometriosis it has been recommended that surgical treatment be preceded by a 3-month course of medical treatment to reduce vascularization and nodular

Postoperative medical treatment is rarely indicated because it does not work based on randomized trials, because it prevents pregnancy, and the highest pregnancy rates occur

For some women, transection of presacral nerves lying within the interiliac triangle may provide relief of chronic pelvic pain. PSN is used in a limited manner and not recommended

Surgical treatment of DIE (Deeply Infiltrating Endometriosis) requires a professional who is able to perform surgery in the gynaecological, urological, gastrointestinal and nervous structures of the pelvis, as the disease 'knows no boundaries'. There is no scientific validation either that a multispecialty team approach is superior for the treatment of bowel endometriosis, which could also make the multisurgeon model 'experimental' and therefore

Preoperative laxatives, starch-free diet, and full bowel preparation are needed to allow perioperative bowel suturing, if needed. Ureter stents may be required before excision of peritoneal endometriosis surrounding the ureter. A multidisciplinary approach involving

Bladder endometriosis is rare .The common clinical manifestations of bladder endometriosis include menouria and urethral and pelvic pain syndrome occurring cyclically. Cystoscopy is the most useful diagnostic test with confirmation by histologic study. Treatment must be individualized according to the patient's age, desire for future pregnancies, the severity of the symptoms, the site affected, and whether other organs are involved. transurethral resection-endometrioma biopsy to confirm the diagnosis and hormone blockade with LH– RH analogues is the initial treatment most commonly used in recent years, despite an

Analogues have been the medical treatment of choice because their introduction, and the estrogens, androgens, progestogens, and danazol used in previous years have fallen into disuse because they lead to more adverse effects. Analogues induce a postmenopause like anovulatory state, a hypogonadotropic hypogonadism with serum estrogen concentrations dropping to sterilization levels, which causes the endometrial tissue to

Ureter endometriosis was related with reproductive tract endometriosis. It has insidious process resulting in difficulty for early diagnosis. It's important to treat pelvic deep infiltrating endometriosis and ovarian endometrioma to prevent ureter from further involvement. Post-operative treatment of pelvic endometriosis is the key point of preventing

gynecologic and gastroenterologic surgeons and urologists is desirable.

Laparoscopic presacral neurectomy can be offered to treat midline pelvic pain.(114, 118)

during the first 6 to 12 months after conservative surgery (116, 117).

routinely for management of endometriosis related pain.

Deep Rectovaginal and Rectosigmoidal Endometriosis:

size (115).

unethical. (119)

regress. (121, 122)

estimated recurrence of 25–35% .(120)

Presacral Neurectomy (PSN):

relapse of ureter endometriosis.(123) The laparoscopic approach for ureteral endometriosis is very well tolerated and has a reasonable incidence of complications, as well as a low rate of recurrence.

Considering the difficulty of achieving a strictly scientific approach to low disease prevalence, the surgeon dealing with ureteral endometriosis must adapt surgery to achieve a balance between conservative purposes and the risk of recurrence on the one hand, and a radical approach and risk of morbidity on the other. Ureterolysis could be used as the initial surgical step for patients with ureteral endometriosis, and may be the only treatment if the extension of ureteral involvement is limited in length and there is no residual ureteral damage or dilatation.

For patients displaying extended severe ureteral involvement, stenosis, or moderate or severe hydronephrosis with a high risk of having intrinsic ureteral disease, ureterolysis is probably insufficient and ureteroneocystostomy likely represents a wiser surgical strategy (124).

Long-term probability of pain recurrence after repeat conservative surgery for recurrent endometriosis varies between 20 and 40%. The association of presacral neurectomy to the treatment of endometriosis might be effective in reducing midline pain; however, no studies have evaluated this procedure among patients with recurrent disease. The medium-term outcome of hysterectomy for endometriosis-associated pain is quite satisfactory; nevertheless, probability of pain persistence after hysterectomy is 15% and risk of pain worsening 3–5%, with a six times higher risk of further surgery in patients with ovarian preservation as compared to ovarian removal. The conception rate among women undergoing repetitive surgery for recurrent endometriosis associated with infertility is 26%, whereas the overall crude pregnancy rate after a primary procedure is 41%.

Repeat conservative surgery for pelvic pain associated with recurrent endometriosis has the same limitations as primary surgery, with long-term cumulative recurrence rates ranging from 20 to 40%. Conversely, only one woman out of four will conceive after repeat conservative surgery for infertility, almost half the pregnancy rate after primary surgery and with no substantial advantages over IVF. (102)

Assisted Reproduction and Endometriosis:

The treatment of endometriosis-related infertility is dependent on the age of the woman, the duration of infertility, the stage of endometriosis, the involvement of ovaries, tubes, or both in the endometriosis process, previous therapy, associated pain symptoms, and the priorities of the patient, taking into account her attitude toward the disease, the cost of treatment, her financial means, and the expected results.

The success of surgery in relieving infertility is probably related to the severity of endometriosis. A recent retrospective multicenter analysis (125) reported cumulative pregnancy rates of 39%, 31%, 30%, and 25% in patients with endometriosis stages I , II, III, and IV, respectively ,l2 months after surgical treatment.

Endometriosis-associated infertility can be successfully treated with intrauterine insemination, but only if it is done in combination with ovarian stimulation (126).

Endometriosis 23

[13] Kennedy S, Bergqvist A, Chapron C, et al: ESHRE guideline for the diagnosis and

[14] Marchino GL, Gennarelli G, Enria R, et al: Diagnosis of pelvic endometriosis with use of

[16] Montalto M, Santoro L, D'Onofrio F, Gallo A, Campo S, Campo V, Gasbarrini A,

[17] Halme J, Hammond MG, Hulka JF, Raj SG, Talbert LM. Retrograde menstruation in

[18] Troyer MR. Differential Diagnosis of Endometriosis in a Young Adult Woman With

[19] Keettel WC, Stein RJ. The viability of the cast-off menstrual endometrium. Am J Obstet

[20] Mungyer G, Willemsen WN, Rolland R, Vemer HM, Ramaekers FC, Jap PH, Poels LG.

[21] Ridley JH, Edwards IK. Experimental endometriosis in the human. Am J Obstet

[22] Signorile PG, Baldi A. Endometriosis: new concepts in the pathogenesis. Int J Biochem

[23] Nisolle M, Donnez J. Peritoneal endometriosis, ovarian endometriosis, and

[25] Matsuura K, Ohtake H, Katabuchi H, et al: Coelomic metaplasia theory of

[26] Mitchell AO, Hoffman AP, Swartz SE, et al: An unusual occurrence of endometriosis

[27] Pollack R, Gordon PH, Ferenczy A, et al: Perineal endometriosis. A case report. J

[28] Wu MH, Shoji Y, Chuang PC, Tsai SJ. Endometriosis: disease pathophysiology and the

[29] Tsai SJ etal.(2001)Regulation of steroidogenic acute regulatory protein expression and

[30] Noble LS. etal. (1996) Aromatase expression in endometriosis. J Clin Endocrinol Metab

[31] Guo SW. Epigenetics of endometriosis. Mol Hum Reprod. 2009 Oct;15(10):587-607.

role of prostaglandins. Expert Rev Mol Med. 2007 Jan 16;9(2):1-20.

[24] Bulun SE. Endometriosis. New England Journal of Medicine.2009;360:268–79.

Gasbarrini G. Endometriosis, need for a multidisciplinary clinical setting: the

healthy women and in patients with endometriosis. Obstet Gynecol. 1984; 64:151–

Cell of the mucous membrane of the female genital tract in culture: a comparative study with regard to the histogenesis of endometriosis. In Vitro Cell Dev Biol. 1987

adenomyotic nodules of the rectovaginal septum are three different entities.

endometriosis: evidence from in vivo studies and an in vitro experimental model.

in the right groin: a case report and review of the literature. Mil Med 156:633,

progesterone production in endometriotic stromal cells. J Clin Endocrinol Metab 86,

treatment of endometriosis. Hum Reprod. 2005; 20(10):2698.

internist's point of view. Intern Emerg Med. 2010; 5(6):463-7.

Nonspecific Low Back Pain. Physical Therapy. 2007; 87(6): 801-10

[15] Farquhar C. Endometriosis. BMJ 2007; 334:249-53

Gynecol. 1951 Feb;61(2):440-2.

Gynecol. 1958 Oct;76(4):783-9

Cell Biol. 2010 Jun;42(6):778-80.

Reprod Med 35:109, 1990

Fertility and Sterility. 1997;68:585–95.

Gynecol Obstet Invest 47(Suppl 1):18, 1999

Feb;23(2):111-7.

1991

5765-5773

81, 174-179

154

macroscopic versus histologic findings. Fertil Steril. 2005; 84:12.

However, there is clear evidence that the pregnancy rate in an insemination program is lower in women with endometriosis than in women with unexplained infertility. (127, 128) More recent studies that reported a normal fertilization rate but a reduced implantation rate per embryo transferred in women obtaining oocytes from donors with endometriosis (129, 130). This reduced implantation rate could be related to increased interleukin-6 levels in follicular fluid of women with endometriosis when compared with controls (131).